Electrochemical devices with plastic substrates

ABSTRACT

An electrochromic device includes a flexible plastic substrate including a front surface, and a rear surface, wherein the rear surface comprises a first conductive material; and a rigid plastic substrate including a front surface, and a rear surface, wherein the front surface comprises a second conductive material, wherein the first substrate is joined to the second substrate by a sealing member, wherein the rear surface of the first substrate and the front surface of the second substrate with the sealing member define a chamber therebetween.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/065,788, filed Mar. 9, 2016, which in turn claims the benefit of U.S.Provisional Patent Application Nos. 62/130,354, filed on Mar. 9, 2015;62/135,003, filed on Mar. 18, 2015; 62/184,704, filed on Jun. 25, 2015;62/257,950, filed on Nov. 20, 2015; and 62/258,051, filed on Nov. 20,2015; the entire disclosures of which are incorporated herein byreference for any and all purposes.

FIELD

The present technology is generally related to electrochromic devices.More particularly, it is related to electrochromic devices having atleast one plastic substrate.

SUMMARY

In one aspect, an electrochromic device includes a first flexible orrigid plastic substrate and a second flexible or rigid plasticsubstrate. The first flexible or rigid plastic substrate includes afront surface and a rear surface, where the rear surface includes afirst conductive material, and the front surface, the rear surface, orboth the front surface and the rear surface of the first substrateincludes a gas diffusion barrier. The second flexible or rigid plasticsubstrate includes a front surface and a rear surface, wherein the frontsurface includes a second conductive material. Over, in the device, thefirst substrate is joined to the second substrate by a sealing member,where the rear surface of the first substrate and the front surface ofthe second substrate with the sealing member define a chambertherebetween. In some embodiments, the front surface, the rear surface,or both the front surface and the rear surface of the second substrateinclude a gas diffusion barrier. In any of the above embodiments, thechamber may include an electrochromic medium including a cathodicmaterial and an anodic material. In any of the above embodiments, thefirst conductive material may include a conductive nanowire coating, aconductive metal mesh, an insulator/metal/insulator stack (IMI stack), atransparent polymer filled with nanoparticles (such as indium tin oxideparticles), carbon nanotubes, graphene, or a conductive polymer. In anyof the above embodiments, the second conductive material may include aconductive nanowire coating, a conductive metal mesh, or an IMI stack.In some embodiments, additional conductive coating may overlay either orboth of the first or second conductive metal meshes or conductivenanowire coating.

In any of the above embodiments, the sealing member may include athermally-curable seal, an ultraviolet-curable seal, a hot melt using athird thermal plastic, a weld, a pressure sensitive adhesive (PSA), or aheat seal film holding the first substrate to the second substrate.

In any of the above embodiments, the chamber may include a firstpolymer-based electrochromic film. In any embodiment descried herein,the polymer-based electrochromic films may be cross-linkedelectrochromic films or thermoplastic electrochromic films. In any ofthe above embodiments, the first polymer-based electrochromic film mayinclude a first electroactive material and a first thermoplasticpolymer. In any of the above embodiments, the first electroactivematerial is a cathodic material, and anodic material, or a mixture of acathodic material and an anodic material.

In any of the above embodiments, the chamber may include a secondpolymer-based electrochromic film. The polymer-based electrochromicfilms may be cross-linked electrochromic films or thermoplasticelectrochromic films. The polymer-based electrochromic film may includea second electroactive material and a second thermoplastic polymer. Inany of the above embodiments, where the device includes both first andsecond polymer-based electrochromic film (e.g., thermoplasticelectrochromic films), the films may be separated by an electrolytelayer. The electrolyte layer may incorporate a porous membrane or anion-exchange membrane capable of ion transport.

In another aspect, an electrochromic device includes a first flexible orrigid plastic substrate having a first surface and a second surface, asecond flexible or rigid plastic substrate having a first surface and asecond surface; and a sealing member, joining the second surface of thefirst substrate to the first surface of the second substrate forming achamber therebetween. In the device, a surface or both surfaces of thefirst substrate is coated with, or the substrate is impregnated with, anultraviolet light absorbing layer or material, the second surface iscoated with a conductive material and a first polymer-basedelectrochromic film including an anodic material, and the chamberincludes a fluid medium containing a UV-curable or thermally-curablegelling agent. In some embodiments, the fluid medium further includes acathodic material. In any of the above embodiments, the fluid medium mayfurther include an ultraviolet absorbing material. In some embodiments,the first surface of the second substrate is coated with a secondpolymer-based electrochromic film including a cathodic material. Inother embodiments, the first surface of the second substrate is coatedwith a conductive coating. The sealing member may include a UV-curableresin, a thermal cure resin, a hot melt plastic, a PSA, a heat sealfilm, or a weld between the first substrate and the second substrate.

In another aspect, an electrochromic device includes a first flexible orrigid plastic substrate and a second flexible or rigid substrate. In thedevice, the first flexible or rigid substrate includes a front surfaceand a rear surface having a conductive nanowire coating, a conductivemetal mesh, an IMI stack, a transparent polymer filled withnanoparticles (such as indium tin oxide particles), carbon nanotubes,graphene, or a conductive polymer, where the front surface, the rearsurface, or both the front surface and the rear surface of the firstsubstrate has a gas diffusion barrier. The conductive wire mesh or theconductive nanowire coating can be coated with another conductivecoating. In the device, the second flexible or rigid plastic substrateincludes a front surface having a conductive nanowire coating, aconductive metal mesh, an IMI stack, a transparent polymer filled withnanoparticles (such as indium tin oxide particles), carbon nanotubes,graphene, or a conductive polymer, and a rear surface, where the firstsubstrate is joined to the second substrate by a sealing member, and therear surface of the first substrate and the front surface of the secondsubstrate with the sealing member define a chamber therebetween. In someembodiments, the second substrate is a plastic substrate and the frontsurface, the rear surface, or both the front surface and the rearsurface of the second substrate include a gas diffusion barrier. Thesubstrates may include an additional coating that absorbs UV light or aUV absorbing material may be incorporated into the substrate. In any ofthe above embodiments, the chamber includes an electrochromic mediumincluding a cathodic material and an anodic material. In any of theabove embodiments, the rear surface of the first substrate includes aconductive nanowire coating, a conductive metal mesh, an IMI stack, atransparent polymer filled with nanoparticles (such as indium tin oxideparticles), carbon nanotubes, graphene, or a conductive polymer; and thefront surface of the second substrate comprises a conductive nanowirecoating, a conductive metal mesh, an IMI stack, a transparent polymerfilled with nanoparticles (such as indium tin oxide particles), carbonnanotubes, graphene, or a conductive polymer. In any of the aboveembodiments, the rear surface of the first substrate and the frontsurface of the second substrate each include a conductive coatingdisposed between the conductive material and the chamber. In any of theabove embodiments, the first surface of the first substrate and/or thesecond surface of the second substrate include a scratch-resistantcoating. Additional coatings applied to a surface may include, but arenot limited to, an anti-reflection coating and/or an anti-smudge oranti-fingerprint coating.

In another aspect, a process is provided for forming a substrate for anelectrochromic device. The process includes coating a surface of a firstflexible or rigid plastic substrate with a first polymer-basedelectrochromic film. The first polymer-based electrochromic film has atleast one first electroactive material and a first thermoplasticpolymer, the first surface further including a conductive nanowirecoating, a conductive metal mesh, an IMI stack, a transparent polymerfilled with nanoparticles (such as indium tin oxide particles), carbonnanotubes, graphene, or a conductive polymer, and a gas barrier coatingon a second surface of the first flexible or rigid plastic substrate.The conductive nanowire coating or conductive metal mesh may be furthercoated with an additional conductive coating. In some embodiments of theprocess, the coating is applied using slot die coating, ink jetprinting, screen printing, gravure coating, curtain coating, spraycoating, dip coating, extrusion coating, or slide coating. In any of theabove embodiments, the process also includes joining the surface of thefirst substrate including the first polymer-based electrochromic film toa first surface of a second substrate with a sealing member, and forminga chamber therebetween. In any of the above embodiments, the processalso includes coating the first surface of the second substrate with asecond polymer-based electrochromic film, the second electrochromic filmincluding at least one second electroactive material and a secondthermoplastic polymer. In any of the above embodiments, the process mayalso include filling the chamber with a fluid or gel electrolyte medium.The fluid medium may be subsequently gelled or solidified in situ.

In another aspect, an electrochromic device includes a flexiblesubstrate including a front surface; and a rear surface; wherein: therear surface comprises a first conductive material; and the frontsurface, the rear surface, or both the front surface and the rearsurface of the first substrate comprises a gas diffusion barrier; arigid substrate including a front surface; and a rear surface; wherein:the front surface comprises a second conductive material; wherein: theflexible substrate is shape conforming to the rigid substrate; theflexible substrate is joined to the rigid substrate by a sealing member,where the rear surface of the flexible substrate and the front surfaceof the rigid substrate with the sealing member define a chambertherebetween.

In another aspect, an electrochromic device includes a rigid substrateincluding a front surface; and a rear surface; wherein: the rear surfacecomprises a first conductive material; and the front surface, the rearsurface, or both the front surface and the rear surface of the firstsubstrate comprises a gas diffusion barrier; a flexible substrateincluding a front surface; and a rear surface; wherein: the frontsurface comprises a second conductive material; wherein: the flexiblesubstrate is shape conforming to the rigid substrate; the flexiblesubstrate is joined to the rigid substrate by a sealing member, wherethe rear surface of the flexible substrate and the front surface of therigid substrate with the sealing member define a chamber therebetween.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic cross-section drawing of an electrochromic device,according to some embodiments.

FIG. 2 is a schematic drawing of a substrate having a conductive layeron one surface, according to some embodiments.

FIG. 3 is a schematic drawing of conductive wires and mesh patterns.

FIG. 4 illustrates the absorbance increase for electrochromic devicesdue to oxygen incursion into the device, according to the workingexamples.

DETAILED DESCRIPTION

Various embodiments are described hereinafter. It should be noted thatthe specific embodiments are not intended as an exhaustive descriptionor as a limitation to the broader aspects discussed herein. One aspectdescribed in conjunction with a particular embodiment is not necessarilylimited to that embodiment and can be practiced with any otherembodiment(s).

As used herein, “about” will be understood by persons of ordinary skillin the art and will vary to some extent depending upon the context inwhich it is used. If there are uses of the term which are not clear topersons of ordinary skill in the art, given the context in which it isused, “about” will mean up to plus or minus 10% of the particular term.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the elements (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. Recitation of ranges of values herein are merely intended toserve as a shorthand method of referring individually to each separatevalue falling within the range, unless otherwise indicated herein, andeach separate value is incorporated into the specification as if it wereindividually recited herein. All methods described herein can beperformed in any suitable order unless otherwise indicated herein orotherwise clearly contradicted by context. The use of any and allexamples, or exemplary language (e.g., “such as”) provided herein, isintended merely to better illuminate the embodiments and does not pose alimitation on the scope of the claims unless otherwise stated. Nolanguage in the specification should be construed as indicating anynon-claimed element as essential.

The term “substantially transparent” as used herein will be understoodby persons of ordinary skill in the art and will vary to some extentdepending upon the context in which it is used. If there are uses of theterm which are not clear to persons of ordinary skill in the art, giventhe context in which it is used, the term means that the material allowsa light transmission of about 75% or more of a beam of light having awavelength of 400 nm directed to the material at a specular angle of 10°through a thickness of 2 mm of the material.

Electrochromic devices having plastic substrates have been desired formany years. The present inventors provide herein a number of solutionsto problems that have plagued the implementation of plastic substrateelectrochromic devices. Such problems include, but are not limited to,oxygen incursion, unavailability of low resistance conductive coatings,ability to cure materials using ultraviolet (UV) light, electrochromicfilms that will flex with the substrate, and methods of making suchmaterials and devices.

The electrochromic devices described herein include at least one chamberdefined by a first substrate having a first conductive surface, a secondsubstrate having a second conductive surface, and a sealing memberjoining the first substrate to the second substrate with the first andsecond conductive surfaces contacting at least a portion of the sealingmember. Within the chamber defined therein, an electrochromic medium maybe disposed, the electrochromic medium providing for a color change ofthe device upon application of a potential to one or both of theconductive surfaces. As used herein, the electrochromic medium maycontain at least a cathodic material (i.e. a material that isreducible), an anodic material (i.e. a material that is oxidizable), ora mixture of a cathodic material and an anodic material. Theelectrochromic medium may be solid state, solution phase, a gel, or apolymer-based material such as a thermoplastic material or across-linked material. One or both of the cathodic and anodic materialsmay be confined to one or both of the first and second substrates. Insome embodiments, where one or both of the cathodic and anodic materialsare surface confined, the anodic material may be sequestered on thefirst or second conductive surface and the cathodic material may besequestered on the second or first conductive surface. Theelectrochromic medium may also contain an electrolyte to facilitatecharge movement from one electrode to the other. The first and secondsubstrates may be off-set to one another to allow for electric contactto be made with the first and second conductive surfaces.

Because these are electrochromic devices, it is understood that when asufficient potential is applied to the device, the electrochromic mediumor coatings undergo a change in transmission. The change in lighttransmission may be the result of a color change in the medium orcoating such that oxidation and reduction of the anodic and cathodicspecies changes the absorption of the medium or coating, resulting in areduction in transmission upon application of the potential. Release ofthe potential may result in maintenance of the reduced transmissionstate when the anodic and cathodic materials are confined with respectto movement through the chamber, or release of the potential may resultin an increase in transmission if the anodic and cathodic materials areallowed to migrate through the chamber or if the reduced cathodic andoxidized anodic are not held separated in the chamber. Shorting of thedevice after application of a potential may speed the time necessary forthe transmission state to return to the original, pre-potential lighttransmission. Momentarily reversing the applied potential may also speedthe change in transmission from low light transmission to high lighttransmission.

Referring generally to FIG. 1, an electrochromic device 100 is provided.The device 100 has a first substrate 110 and a second substrate 120,each substrate having a front surface and a rear surface. The firstsubstrate 110 will be joined to the second substrate 120 by a sealingmember 130 such that a chamber is formed. The chamber is defined by therear surface of the first substrate 110, the front surface of the secondsubstrate 120, and an inner surface of the sealing member 130. Asillustrated in FIG. 2, the rear surface of the first substrate 110 mayinclude a first conductive material 112. The device may be a mirror,where the first substrate is substantially transparent and the secondsubstrate is a mirrored substrate, with the front or rear surface beingthe mirrored surface. The device may also be a window, such as anarchitectural window, car window, or aircraft window, where bothsubstrates are substantially transparent. The device may also be a lightfilter. The device may also be an eyewear lens. The devices may also bemirrored, moderately transparent, or substantially transparent, flexibleor rigid electrochromic devices for any other particular application.

Gas Diffusion Barrier

In the device, the front surface, the rear surface, or both the frontand rear surfaces of the first substrate include a gas diffusionbarrier. The gas diffusion barrier is a barrier to incursion of gas,such as oxygen or water vapor, into the device. Thus, the gas diffusionbarrier prevents, or at least limits, gas from entering the devices.Where the second substrate is made of a material (vide infra) that ispermeable, the front surface, the rear surface, or both the front andrear surface of the second substrate may also include a gas diffusionbarrier. It is preferred to have the gas barrier on the substratesurface that is closest to the electrochromic media. For example, theback surface of the first substrate and/or the front surface of thesecond substrate.

Wherever a gas diffusion barrier is employed in the device, the gasdiffusion barrier may minimize or prevent the incursion of the gas intothe device. For example, where the gas to be excluded by the diffusionbarrier is oxygen, the gas diffusion barrier prevents, or at leastminimizes, the incursion of oxygen into the device. Where the gas to beexcluded is water vapor, the gas diffusion barrier prevents, or at leastminimizes, the incursion of water into the device. In some embodiments,the gas diffusion barrier is a barrier to a single gas, while in otherembodiments, the gas diffusion barrier is a barrier to multiple gases.This may be provided by a single layer gas diffusion barrier or multiplelayer gas diffusion barriers. For an electrochromic device the substrateand gas barrier should have an oxygen transmission rate that is lessthan 10⁻² cm³/m²/day atm. This may include less than 10⁻³ cm³/m²/day atmand less than 10⁻⁴ cm³/m²/day atm

Illustrative gas diffusion barriers may include a polymer and/orinorganic film(s) that is applied to the substrate, layer(s) applied tothe substrate by physical vapor deposition such as vacuum evaporation orsputtering, plasma-enhanced chemical vapor deposition (PECVD); layer(s)applied by atomic layer deposition (ALD); or layer(s) applied to thesubstrate by neutral beam assisted sputtering (NBAS). Illustrativebarrier films may include, but are not limited to, those of Al₂O₃,Si₃N₄, SN, TiN, SiO_(x)N_(y), indium tin oxide (ITO), SiO₂, ZnO₂, orTiO₂, where x and y are from greater than 0 to 4. Where the gasdiffusion layer is a polymer; illustrative polymers may include, but arenot limited to, a polyimide, a polyester (such as polyethyleneterephthalate (PET) and/or polyethylene naphthalate (PEN)), acycloolefin copolymer (COC), a cycloolefin polymer (COP), apoly(ethylene-co-vinyl alcohol) (EVOH), acrylates, methacrylates, apolyvinyl alcohol (PVOH), Saran® (PVDC), Saranex® (HDPE, EVA, and PVDC),epichlorohydrin, Barex® (an acrylonitrile copolymer). Other illustrativebarriers include films of self-assemble nanoparticles (SNAPs),multilayer mixed organic and inorganic thin films, such as, but notlimited to, Vitex® barrier systems, Fujifilm barriers, and 3M barriers.The Vitex system is a film of alternating layers of DC reactivesputtered aluminum oxide and vapor deposited organic monomers that areUV-cured. Fujifilm and 3M systems are similar to the Vitex, in that theyare alternating films of inorganic and polymer films. The multilayerbarrier films are generally composed of alternating organic (usuallyacrylates) and inorganic (metal oxides or nitrides) layers (dyads) on apolyethylene terephthalate or polyethylene naphthalate substrate.Commercially available barrier films generally have 2 to 3 dyads and aprotective topcoat. Another illustrative barrier system is alternatingthin films of cationic and anionic polymers deposited by layer-by-layerdeposition techniques, as illustrated by reference: Yang, Y. H. et al.Macromol, 2011, 44, 1450-1459. Another illustrative barrier filmincludes a flexible, thin glass films (less than 0.5 mm thick) appliedto the plastic substrate. The thin glass may be adhered to the plasticsubstrate using liquid optical coupling adhesives or laminated usingoptically clear pressure sensitive adhesives. An example of a suitableflexible, thin glass film includes, but is not limited to, Willow® glassavailable from Corning Inc. (Corning, N.Y.).

Substrates

In the device, at least the first substrate is a plastic substrate. Theplastic substrate may be a polymeric substrate that includes, but is notlimited to, polyethylene (both low and high density), polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC),polysulfone, acrylic polymers including, but not limited topolymethylmethacrylate (PMMA), polymethacrylates, polyamides including,but not limited to, a cycloaliphatic diamine dodecanedioic acid polymer(i.e. Trogamid® CX7323), epoxies, cyclic olefin polymers (COP) such asZeonor 1420R, cyclic olefin copolymers (COC) such as Topas 6013 S-04 orMitsui Apel, polymethylpentene, cellulose ester based plastics likecellulose triacetate, and polyacrylonitrile. With regard to the secondsubstrate, it may be a plastic substrate of the same, or a differentpolymeric material than the first substrate. Where both the first andsecond substrates are plastic substrates, they may be flexible or rigidsubstrates such that the electrochromic device formed therefrom is aflexible or rigid electrochromic device.

One issue that is prevalent with transparent conductive oxide (TCO)coatings on a plastic substrate is the inability to achieve asufficiently low sheet resistance for an electrochromic device. The rear(or second) surface of the first substrate and the front (or first)surface of the second substrate include a conductive material. Where thesecond substrate is a metal, the sheet resistance is sufficiently low,however for the first substrate, which is a substantially transparentsubstrate, the rear surface includes a conductive material to provide aconductive surface on the substrate. For example, the conductivematerial may be a TCO such as indium tin oxide (ITO), indium zinc oxide(IZO), zinc oxide, and tin oxide. However, where flexibility is to beexhibited by at least the first substrate, and particularly where bothsubstrates are flexible or rigid, indium tin oxide is quite brittle andmay not survive repeated flexing. Accordingly, in the present technologythe conductive material may be a conductive nanowire coating orconductive metal mesh material that has dimensions such that it does notsubstantially affect the reflection in the case of a mirror or thetransparency in the case of a window. For example, the mesh or nanowirecoating may have a transmission that is greater than 50%. In any of theabove embodiments, the mesh may have a transmission that is greater than60%, greater than 70%, greater than 80%, or greater than 90%. Theconductive material may also be an insulator/metal/insulator stack (an“IMI stack”) such as those disclosed in U.S. Pat. Nos. 7,830,583 and8,368,992. The insulator may be a TCO such as ITO and the metal may be aconductive metal such as silver. Such structures are able to obtain asheet resistance of 5 to 9 Ω/sq while having a transmission higher than80% and a thickness lower than 110 nm, which is much smaller than an ITOcoating on plastic having 5 Ω/sq at 860 nm thickness. Further, the mesh,nanowire coating, and or IMI stack may have a sheet resistance of lessthan 50 Ω/sq. This may include a sheet resistance of less than 10 Ω/sq,less than 1 Ω/sq, less than 0.5 Ω/sq, less than 0.2 Ω/sq, less than 0.1Ω/sq, less than 0.05 Ω/sq, or less than 0.01 Ω/sq. In any of the aboveembodiments, the mesh may have a sheet resistance of from about 0.0001Ω/sq to about 50 Ω/sq. This may include meshes, nanowire coatings, andIMI stacks having a sheet resistance from about 0.0001 Ω/sq to about 10Ω/sq, from about 0.0001 Ω/sq to about 5 Ω/sq, from about 0.0001 Ω/sq toabout 1 Ω/sq, from about 0.001 Ω/sq to about 10 Ω/sq, and from about0.001 Ω/sq to about 1 Ω/sq. A brittle TCO such ITO may be coated (eitherundercoated, overcoated, or both) with a more flexible conductive filmlike a conductive polymer or a transparent polymer filled withconductive nanoparticles (such as ITO nanoparticles) to make it moreresistant to substrate flexing. If cracks develops in the brittle TCOthe flexible conductive film will electrically bridge the gap andmaintain conductivity in the damaged area.

One problem with coatings on plastic substrates, in particular onsubstrates that tend to be chemically inert, such as COCs or COPs, isthat without an adhesion promotion layer or substrate surface activationprior to applying the gas diffusion barriers and conductive coatings,the coatings on the substrate would be prone to have areas withdelamination. The delamination of the coatings from the substrateprovides channels for the penetration of oxygen or water vapor into theelement chamber, in particular if there is delamination near the seal.Alternatively, delamination happening near the center of the EC devicealso would cause openings for oxygen or water vapor in the gas diffusionbarrier and therefore defeating its purpose. Accordingly, the adhesionpromotion layer may be a translucent layer of a metal coating such asaluminum, titanium, copper or chromium, preferably chromium, coatedpreferably using magnetron sputtering, with a thickness lower than 20nm, preferably lower than 5 nm, and a transmission that is greater than50%. A polymer based adhesion promotion layer or primer may be employedsuch as a polyimide coating. The substrate may be surface activatedprior to coating using a plasma jet at atmospheric pressure, such ascorona plasma. using a mixture of gases such as nitrogen, argon andoxygen. Another option is the use of ion beam etching in a vacuumenvironment, also using gases such as oxygen and nitrogen, where the ionenergy can be between 100 to 5000 keV and the ion dosage at the 1×10¹⁴to 1×10¹⁸. Other options for surface activation are oxygen plasma etchand ultraviolet light in ozone atmosphere. Yet another option for theactivation of the surface is the use of flame treatment, and the use ofSiO₂ flame pyrolysis treatment.

Illustrative nanowires coatings or conductive metal mesh materialsinclude, but are not limited to silver, gold, stainless steel, aluminum,copper, nickel, molybdenum, tungsten, iridium, rhodium, ruthenium,platinum, cobalt, palladium, chromium, titanium, and alloys thereof.Nanowire based films can be formed via solution coated chemistry,printing processes, photographic technologies, rolling lithography, orself-assembly. Examples of films via solution coated chemistry includeClearOhm™ from Cambrios Technologies Corporation (10-300 Ω/□, >80% T)and Flexx™ from Carestream Advanced Materials (10-100 Ω/□, >80% T).These films are based on PET. A nanowire based film produced viaself-assembly is Sante® from Cima NanoTech (10-100 Ω/sq, >80% T).Conductive metal mesh films are produced using a wide array ofprocessing including printing, rolling lithography, and photographictechnology. Exclucent™ film (<0.1 Ω/sq, 80% T) from Applied Nanotech isproduced through a printing process. NanoWeb™ metal mesh (5 Ω/sq, >80%T) from Rolith Inc. is produced through rolling lithography. Fujifilmoffers a Exclear™ metal mesh (1-50 Ω/sq, >80% T) that is produced usinga silver halide photographic process.

The nanowire based films have the advantage of a random pattern whichminimizes moire issues. The repeating pattern of the metal meshconductors is prone to moire issues and requires the proper orientationof overlapping films to minimize the effect.

One major issue with a repeating pattern such in a metal wire meshconductor is that when illuminated with a near point light source suchas a headlamp, street light or the sun an intense diffraction patterncan be seen when viewed through the conductor in transmission and/orreflection. The pattern can be severe enough to make the conductorunusable in many commercial applications such as windows for buildingsand aerospace and auto dimming rearview mirrors. The visibility of thediffraction pattern can be minimized by varying the spacing between themetal lines in the mesh, by varying the width of the metal lines in themesh pattern, by continuously varying the angle of the mesh linesrelative to one another so the relative distance between the linesvaries or by making the size of the metal mesh features (mesh spacingand metal line width) large enough or small enough to not creatediffraction patterns in the visible light range. Another way to reducethe visible intensity of these diffraction patterns is to render themetal surface black or non-reflective such that it will absorb lightincident upon it. This can be done in a number of ways such as byprinting a black ink under the metal mesh, on top of the metal mesh orboth or by forming black dendritic layer of nickel or chrome or othermetal on the surface of the metal mesh. The black light absorbingpatterned coatings could be applied on top of or under a secondcontinuous conductive coating if one is applied over or under the metalmesh layer. For electrochromic device applications it is preferred thatthe black coating that is applied on top of the metal mesh beconductive.

In other embodiments, the pattern of mesh on one substrate may be offsetfrom the pattern on the second substrate. For example, the meshes may beoffset by from 10 to 80 degrees. Or, the pattern may be varied such thatthe wires in one direction are not regularly spaced such that there is arandomized variation of conductive material across the surface of thesubstrate. FIG. 3 illustrates various patterns of deposition of theconductive meshes or coatings and the offsets.

Depending on the electrochromic device configuration, it may bepreferred to have higher conductivity or lower resistance in onedirection than the other. Typically the higher conductivity would beoriented perpendicular to a high conductivity electrical bus, which isusually to be located at a perimeter of an electrochromic device. Thiscan be achieved by orienting more nanowires perpendicular to the busthan parallel to the bus, or by having a wire mesh patter with more meshline perpendicular to the bus or wider line perpendicular to the bus, orthicker lines perpendicular to the bus. In this way, the device wouldcolor more quickly with no, or minimal, loss in transmission. The ratioof resistance perpendicular to the bus to the resistance parallel to thebus may be about 10% or greater, or 20% or greater, or 50% or greater.For flexible substrates that may be repeatably bent, a mesh patternother than straight line that intersect at a 90 degree angle ispreferred to impart flexiblitly and stretchability. Lines that intersectat angles less than 90 degrees and/or lines that incorporate a curved orsquiggle pattern that impart stretchability into the mesh are preferred.

In another embodiment, the conductive layer may be a metal sheet that isapplied to the substrate in a very thin layer. For example, a copper,silver, or gold sheet may be applied using an inkjet technology, wherethe sheet has a transmission of greater than 50% and a resistance of 0.1Ω/sq, or less. This includes where the sheet has a transmission ofgreater than 60%, 70%, or 80%. This includes where the sheet has atransmission of 50% to 90%, or any range therebetween.

It should be noted that applying the metal pattern by inkjet technologyis referred to as an additive process. Other additive printing processesinclude gravure printing and screen printing. Subtractive methods can beused to form the pattern using etching or laser ablation.

Although the metal mesh conductors have a very low sheet resistance, thedensity of the metallic traces is not high enough to prevent selectivecoloring around the traces. To further assist in the transfer of chargefrom the substrate and conductive material to the chamber and theelectrochromic medium confined therein, and to protect the metal meshfrom dissolution into the electrochromic medium during cycling, aconductive coating may be applied over the conductive nanowire coatingor conductive metal mesh. The coating can be applied over the metal onlyto protect it or it can be over the metal and the substrate not coveredby the metal. The coating between the metals may have a sheet resistanceof less than 10,000 Ω/sq. This may include less than 1,000 Ω/sq, lessthan 100 Ω/sq, or less than 10 Ω/sq. Illustrative conductive coatingmaterials include, but are not limited to, a thin metal coating such asgold, a transparent conductive metal oxide (e.g., indium tin oxide(ITO), indium zinc oxide (IZO), zinc oxide, and tin oxide), graphene,carbon nanotubes, or a conductive polymer such aspoly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS),polythiophenes, polyanilines, polyacetylenes, polypyrroles, andpolyphenylene vinylenes. For example, the material may be indium tinoxide, indium zinc oxide, graphene, or carbon nanotubes.

Another issue with TCO coatings is that typical TCO's such as ITOrequire a thermal treatment in order to reach the highest conductivityof the material. On plastics, the temperature of the thermal treatmentsare very limited due to the low glass transition temperature of thesubstrate, which are typically under 100° C. Thus, another disadvantageof TCO's on plastics is that the material has a sub-optimal conductivitydue to the thermal restrictions, between 3 to 5 times lower thanthermally treated ITO. In order to reach a low sheet resistance, thethickness of the TCO needs to be increased to compensate for thedecreased electrical conductivity. A problem with brittle films such asTCOs is that as the film gets thicker, the coating becomes moresensitive to bending—in other words for the same amount of bending, athick coating will fail earlier than a thinner coating, and therefore athinner coating with same sheet resistance as a thicker coating ispreferable. The electrical sheet resistance of a TCO such as ITO can belowered without significantly heating the substrate by flash treatingthe TCO with a high intensity light pulse from a xenon lamp or a laser.This treatment allows for thinner TCO coatings at the same sheetresistance as thicker untreated coatings.

In another aspect, any of the above electrochromic devices is providedfurther including an ultraviolet light-absorbing film on the firstsubstrate. Such a film may be included on the front surface or the rearsurface of the first substrate. An ultraviolet light-absorbing materialmay also be incorporated directly into the plastic substrate materialitself when formed. As will be illustrated below, the electrochromicmedium may include an ultraviolet light-absorbing material to prevent,or at least minimize, degradation of the electrochromic medium andplastic substrate by ultraviolet light. For the purposes of thisparticular discussion with regard to the application of an ultravioletlight-absorbing film, the first substrate is the substrate to be facingan ultraviolet light source. For example, if the electrochromic deviceis a window, the first substrate is the substrate that will be exposedto the outside of the building, and subject to incident light from thesun. Accordingly, the first surface of the first substrate may includethe ultraviolet light-absorbing film. Alternatively, or in addition to,the second surface of the first substrate may include an ultravioletlight-absorbing material. Each substrate itself may include aultraviolet light-absorbing material. This will provide for twoadvantages.

The first advantage is related to preservation of the electrochromicmedium. The electrochromic medium may be sensitive to degradation byultraviolet light. Accordingly, the ultraviolet-absorbing film mayprotect the electrochromic medium from ultraviolet light exposurethrough the first substrate. The second advantage is to allow for theability to UV-cure some of or all of the electrochromic medium by UVlight exposure through the second substrate that has higher UVtransmission. Electrochromic media may be gelled to prevent movement ofthe electrochromic medium within the device, leakage from the device inthe event of breakage, or to provide a unitary structure by binding ofthe first substrate to the second substrate. However, in many cases theelectrochromic medium includes dissolved ultraviolet light-absorbingspecies; therefore gels that are curable using ultraviolet light cannotbe employed. Use of an ultraviolet light-absorbing film on the firstsubstrate allows for the electrochromic medium to include lesser amountsof ultraviolet light-absorbing species or no ultraviolet light-absorbingspecies while allowing for curing an ultraviolet light-curable gel asthe electrochromic medium, as it may be activated by illuminating withultraviolet light through the second substrate for a time sufficient toproduce a gel in the chamber. Materials that are used to seal theperimeter of the EC device can also be UV cured in this manner.

Any of the plastic substrates described herein may include ascratch-resistant coating on the surface to prevent or at least minimizeto the extent possible damage to the outer surfaces of the devices. Insome embodiment, the devices have a scratch resistant coating on theouter surfaces of the device, while a gas diffusion barrier is includedon an inner surface(s) of the device such that the plastic substrateprovides a first barrier to gas incursion into the device, while the gasdiffusion barrier provides a second barrier to gases that reach throughthe plastic substrate.

Other coatings on any of the devices can include anti-fingerprintcoatings, anti-fogging coatings, and anti-smudge coatings andanti-reflection coatings.

Electrochromic Media

The electrochromic medium may take a number of different forms such asthermoplastic polymeric films, solution phase, or gelled phase.Illustrative electrochromic media are those as described in U.S. Pat.Nos. 4,902,108; 5,888,431; 5,940,201; 6,057,956; 6,268,950, 6,635,194and 8,928,966, and U.S. Patent Application Publication No. 2002/0015214.The anodic and cathodic electrochromic materials can also includecoupled materials as described in U.S. Pat. No. 6,249,369. And, theconcentration of the electrochromic materials can be selected as taughtin U.S. Pat. No. 6,137,620. Additionally, a single-layer, single-phasemedium may include a medium where the anodic and cathodic materials areincorporated into a polymer matrix as is described in InternationalPatent Application Serial Nos. PCT/EP98/03862 and PCT/US98/05570.

The electrochromic medium may be multilayer or multiphase. Inmultilayered, the medium may be made up in layers and includes anelectroactive material attached directly to an electrically conductingelectrode or confined in close proximity thereto which remains attachedor confined when electrochemically oxidized or reduced. In multiphase,one or more materials in the medium undergoes a change in phase duringthe operation of the device, for example a material contained insolution in the ionically conducting electrolyte forms a separate layeron the electrically conducting electrode when electrochemically oxidizedor reduced.

The electrochromic medium may include materials such as, but not limitedto, anodics, cathodics, light absorbers, light stabilizers, thermalstabilizers, antioxidants, thickeners, viscosity modifiers, tintproviding agents, redox buffers, and mixtures thereof. Suitable redoxbuffers include, among others, those disclosed in U.S. Pat. No.6,188,505. Suitable UV-stabilizers may include: 2-ethyl-2cyano-3,3-diphenyl acrylate, (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate, 2-(2′-hydroxy-4′-methylphenyl)benzotriazole,3-[3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl]propionicacid pentyl ester, 2,4-dihydroxybenophenone,2-hydroxy-4-methoxybenzophenone, 2-ethyl-2′-ethoxyalanilide, and thelike.

According to some embodiments, the anodic materials may include, but arenot limited to, ferrocenes, ferrocenyl salts, phenazines,phenothiazines, and thianthrenes. Illustrative examples of anodicmaterials may include di-tert-butyl-diethylferrocene;5,10-dimethyl-5,10-dihydrophenazine (DMP);3,7,10-trimethylphenothiazine, 2,3,7,8-tetramethoxy-thianthrene,10-methylphenothiazine, tetramethylphenazine (TMP), andbis(butyltriethylammonium)-para-methoxytriphenodithiazine (TPDT). Theanodic materials may also include those incorporated into a polymer filmsuch as polyaniline, polythiophenes, polymeric metallocenes, or a solidtransition metal oxide, including, but not limited to, oxides ofvanadium, nickel, iridium, as well as numerous heterocyclic compounds.Other anodic materials may include those as described in in U.S. Pat.Nos. 4,902,108; 6,188,505; and 6,710,906.

In any of the above aspects, the anodic material may be a phenazine, aphenothiazine, a triphenodithiazine, a carbazole, an indolocarbazole, abiscarbazole, or a ferrocene confined within the second polymer matrix,the second polymer matrix configured to prevent or minimize substantialdiffusion of the anodic material in the activated state. As with theviologen, the anodic material may be sequestered within the polymermatrix by being physically trapped within, or the anodic material may befunctionalized such that it is amenable to being polymerized or reactedwith the polymer to be covalently bonded to the polymer.

In some embodiments, the anodic material may be a compound representedby:

In the above formula, E is S or NR¹⁰; R¹ and R¹⁰ are individually analkyl group interrupted by at least one ammonium group; R²-R⁹ areindividually H, F, Cl, Br, I, CN, OR¹¹, SR¹¹, NO₂, alkyl, aryl, amino,or any two adjacent groups of R²-R⁹ may join to form a monocyclic,polycyclic, or heterocyclic group; each R¹¹ is individually H or alkyl;and R¹² is an alkylene group. In some embodiments, E is NR¹⁰ and R²-R⁹are H or OR¹¹. In other embodiments, E is S and R⁷ and R⁸ join to form aheterocyclic group.

The anodic material may be a compound represented by:

In the above formula, R¹⁴ is an alkyl group interrupted by at least oneammonium group. In any of the compounds described above, R¹, R¹⁴, andR¹³ may be represented by:

where R¹⁵-R¹⁸ are individually H or alkyl; n is 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, or 12; n′ is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12; and xis 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In some embodiments, n is4, x is 2, and n′ is 11.

Cathodic materials may include, for example, viologens, such as methylviologen, octyl viologen, or benzyl viologen; ferrocinium salts, such as(6-(tri-tert butylferrocenium)hexyl)triethylammonium. It will beappreciated that all such species name only the cationic portion of themolecule and a wide variety of anions may be used as the counterion(s).While specific cathodic materials have been provided for illustrativepurposes only, numerous other conventional cathodic materials arelikewise contemplated for use including, but by no means limited to,those disclosed in previously referenced and incorporated U.S. Pat. No.4,902,108, U.S. Pat. No. 6,188,505, and U.S. Pat. No. 6,710,906.Moreover, it is contemplated that the cathodic material may include apolymer film, such as various polythiophenes, polymeric viologens, aninorganic film, or a solid transition metal oxide, including, but notlimited to, tungsten oxide.

Illustrative cathodic materials, for use in any of the devices describedherein, include viologens and metal oxides. Illustrative metal oxidesinclude those that are electrochromic such as tungsten oxide. Tungstenoxide may act as both a cathodic material as well as a conductivematerial.

In any of the above aspects, the cathodic material may be a viologen ora non-dimerizing or low-dimerizing viologen. Illustrative viologensinclude, but are not limited to, methyl viologen, octyl viologen, benzylviologen, polymeric viologens, and the viologens described in U.S. Pat.Nos. 7,372,609; 4,902,108; 6,188,505; and 6,710,906. Other viologens mayinclude those of Formula (I), (III), or (IV):

In Formula I, R¹ and R² are individually alkyl, siloxy alkyl,hydroxyalkyl, alkenyl, or aralkyl; R⁴, R⁶, R⁸, and R¹⁰ are individuallyH, OH, F, Cl, Br, I, CN, NO₂, alkyl, or aryl; R³, R⁵, R⁷, and R⁹ areindividually H, OH, F, Cl, Br, I, CN, NO₂, alkyl, or aryl, and X is ananion. However, Formula (I) is subject to the proviso that R³ and R⁵, orR⁷ and R⁹, or R³, R⁵, R⁷, and R⁹ are individually secondary alkyl,tertiary alkyl, or aryl. Formula (III):

In Formula (III), R¹ and R² are individually alkyl, siloxyalkyl,hydroxyalkyl, alkenyl, or aralkyl; R⁴, R⁶, R⁸, R¹⁰ are individually H,OH, F, Cl, Br, I, CN, NO₂, alkyl, or aryl; R³, R⁵, R⁷, and R⁹ areindividually H, OH, F, Cl, Br, I, CN, NO₂, alkyl, or aryl; R¹⁹ is(CH₂)^(n′) or arylene, and n′ is from 1 to 12; X is an anion; andwherein R³, and R⁵, or R⁷, and R⁹ are individually secondary alkyl,tertiary alkyl, or aryl. Formula (IV)

In Formula (IV), R¹ and R^(1′) are individually alkyl, siloxyalkyl,hydroxyalkyl, alkenyl, or aralkyl; R⁴, R⁶, R⁸, R¹⁰, R^(4′), R^(6′),R^(8′), and R^(10′) are individually H, OH, F, Cl, Br, I, CN, NO₂,alkyl, or aryl; R⁷, R⁹, R^(7′), and R^(9′) are individually H, OH, F,Cl, Br, I, CN, NO₂, alkyl, or aryl; R¹⁹ is (CH₂)_(n′) or arylene, and n′is from 1 to 12; X is an anion; and either R³, R⁵, R^(3′), and R^(5′)are individually secondary alkyl, tertiary alkyl, or aryl; R⁷, R⁹,R^(7′), and R^(9′) are individually secondary alkyl, tertiary alkyl, oraryl. In some embodiments, for the non-dimerizing electrochromiccompound represented by Formula (IV), R¹⁹ is (CH₂)_(n′) or arylene, andn′ is from 1 to 12. For any of the viologens described, the counterion(anion) may be any of a halide, a borate, a fluoroborate, a tetraarylborate, a hexafluoro metal or metalloid, a sulfate, a sulfonate, asulfonamide, a carboxylate, a perchlorate, a tetrachloroferrate, or thelike, or mixtures of any two or more thereof. Illustrativecounterions/anions include, but are not limited to: F, Cl⁻, BC, I⁻, BF₄⁻, PF₆ ⁻, AsF₆ ⁻, ClO₄ ⁻, SO₃CF₃ ⁻, N(CF₃SO₂)₂ ⁻, C(CF₃SO₂)₃ ⁻, triflate(trifluoromethansulfonate), N(SO₂C₂F₅)⁻, or BAr₄ ⁻, wherein Ar is anaryl or fluorinated aryl or a bis(trifluoromethyl)aryl group. In someembodiments, X is a tetrafluoroborate or a bis(trifluoromethylsulfonyl)imide anion.

The cathodic material may be a protic soluble electrochromic material(e.g., soluble in a protic solvent such as an alcohol and/or water), ora single component electrochromic material (i.e., the electrochromicmaterial includes a compound that includes both cathodic and anodicmoieties in the same molecule or cation/anion combination), such asdescribed in U.S. Provisional Appl. No. 62/257,950, filed on Nov. 20,2015, and 62/258,051, filed on Nov. 20, 2015.

Further examples of anodic and cathodic materials may be found in U.S.Pat. Nos. 4,902,108; 5,294,376; 5,998,617; 6,193,912; and 8,228,590.

For illustrative purposes only, the concentration of the anodic and/orcathodic materials in the electrochromic medium can range fromapproximately 1 millimolar (mM) to approximately 500 mM and morepreferably from approximately 2 mM to approximately 100 mM. Whileparticular concentrations of the anodic as well as cathodic materialshave been provided, it will be understood that the desired concentrationmay vary greatly depending upon the geometric configuration of thechamber containing the electrochromic medium.

For purposes of the present disclosure, a solvent of electrochromicmedium may comprise any of a number of common, commercially availablesolvents including 3-methylsulfolane, dimethyl sulfoxide, dimethylformamide, tetraglyme and other polyethers; alcohols such asethoxyethanol; nitriles, such as acetonitrile, glutaronitrile,3-hydroxypropionitrile, and 2-methylglutaronitrile; ketones including2-acetylbutyrolactone, and cyclopentanone; cyclic esters includingbeta-propiolactone, gamma-butyrolactone, and gamma-valerolactone;organic carbonates including propylene carbonate (PC), ethylenecarbonate and methyl ethyl carbonate; and mixtures of any two or morethereof.

The electrochromic medium may include a thermoplastic polymer in whichthe electrochromic materials are confined (an “electrochromicthermoplastic”). Such media are described in U.S. ProvisionalApplication No. 62/184,704, filed on May 25, 2015. Such media mayinclude a thermoplastic polymer, an electrochromic material, and asolvent or plasticizer, where the thermoplastic polymer is present in anamount sufficient to form a substantially formable gel matrix of theelectrochromic materials (i.e. the matrix contains solvent, but it isself-supporting, moldable, and formable). Such media are prepared bydissolving the thermoplastic polymer under heating in the solvent, andalso dissolving the electrochromic material in the solvent. Upon coolingthe thermoplastic polymer sets up forming a formable gel material. Theformable gel material may be molded or cut to size.

The formable gel material may contain as the electrochromic material acathodic material, an anodic material, or both a cathodic and an anodicmaterial. Where the electrochromic material is either only cathodic oronly anodic, the device may be prepared in a sandwich style such thatthe first substrate may be associated with a thermoplastic polymermaterial including the cathodic material, and the second substrate isassociated with the anodic thermoplastic material, with the twosubstrates joined with or without an electrolyte layer between theseparate sides. In other words, the cathodic material is confined in onehalf of the device, while the anodic material is confined in the otherhalf of the device, with or without a separate electrolyte layer orion-exchange membrane or porous membrane therebetween. In someembodiment, the thermoplastic material may include only an anodicmaterial and is associated with a first substrate, while the secondsubstrate contains a cathodic coating, such as a metal oxide coating. Ofcourse, the thermoplastic material may contain both an anodic materialand a cathodic material.

As noted above, the formable gels may be formed by dissolving thethermoplastic material in the solvent, along with the electrochromicmaterial, and any other additives that are desired, such aselectrolytes, UV absorbing materials, electrochromic buffers, and otherstabilizers. Once the solution of the thermoplastic material isprepared, it may be poured into a mold, a layer drawn with a draw knifeto a desired thickness, or placed between release layers such that itmay be rolled to a desired thickness. The molding or pouring may be ontoa release liner such that after the material cools and sets up as aformable gel, the release liner may be released from the nowelectrochromic thermoplastic matrix. The resulting formable gel may becut or trimmed to the desired shape.

The thermoplastic electrochromic films may be formed by dissolving athermoplastic polymer and an electrochromic material, and optionallyother additives, in a solvent to form a film-forming composition. Thedissolution of the materials may be conducted at elevated temperature.For example, illustrative elevated temperatures may be from about 30° C.to about 150° C. The thermoplastic polymer is included in the solvent ata concentration such that upon cooling the thermoplastic polymer forms aself-supporting matrix, the matrix holding the solvent, theelectrochromic material, and, if present, any optional additives. Toform the film, upon dissolution, but prior to setting up of theself-supporting matrix, the film-forming composition may be cast on aconductive substrate, or the film-forming composition may be cast on arelease liner. Upon cooling, a self-supporting film of the thermoplasticpolymer, electrochromic material, and the optional additives is formed.Where a release liner is used, once the film-forming composition isapplied to the release liner, a second, overlaying release liner may beapplied, the film-forming composition sandwiched therebetween, and theentire assembly put through an extruding press or roller system, suchthat a thermoplastic electrochromic film of uniform thickness is formed.The release liner may then be removed and the film applied to aconductive surface of a first substrate, whereupon the second releaseliner may be removed and a conductive surface of a second substrateapplied. Upon edge sealing the electrochromic is thus formed.

Where the electrochromic device has been constructed using athermoplastic film, further post-treatment could be envision whereadditional crosslinking of the thermoplastic is carried out to increasethe long term mechanical stability of the thermoplastic film, thusproducing a cross-linked electrochromic film. This may be carried outthrough additional UV curing of the thermoplastic film.

Where the electrochromic device includes more than one thermoplasticfilm and/or cross-linked electrochromic film, for example a firstthermoplastic film containing a cathodic material, and a secondthermoplastic film containing an anodic material, the first and secondthermoplastic films may be separated by an ion-exchange or porousmembrane, or a third thermoplastic film to separate the first and secondfilms. The third thermoplastic film may contain an electrolyte or saltsto assist in conduction between the first and second films. Similarly, afirst cross-linked film containing a cathodic material, and a secondcross-linked film containing an anodic material, the first and secondcross-linked films may be separated by an ion-exchange or porousmembrane, or a third film that is either thermoplastic or cross-linkedto separate the first and second films. The third film may contain anelectrolyte or salts to assist in conduction between the first andsecond films. As further example, a first thermoplastic film containinga cathodic material, and a second cross-linked film containing an anodicmaterial, the first and second films may be separated by an ion-exchangeor porous membrane, or a third film that is either thermoplastic orcross-linked to separate the first and second films. The third film maycontain an electrolyte or salts to assist in conduction between thefirst and second films. Yet another example includes a firstcross-linked film containing a cathodic material, and a secondthermoplastic film containing an anodic material, the first and secondfilms may be separated by an ion-exchange or porous membrane, or a thirdfilm that is either thermoplastic or cross-linked to separate the firstand second films. The third film may contain an electrolyte or salts toassist in conduction between the first and second films.

The electrochromic material included in the polymer-based electrochromicfilms may be a cathodic material, an anodic material, or both a cathodicand an anodic material. Thus, the possible combinations are numerous fordifferent situations. The polymer-based electrochromic film may containvarious materials for various applications. As a non-limitingillustration, the polymer-based electrochromic film may contain all ofthe components necessary for an electrochromic device such that the filmmerely need be disposed between conductive substrates such that apotential may be applied to the device to effect the color change.

Illustrative thermoplastic polymers include, but are not limited to,acrylates, methacrylates, polyesters, polycarbonates, polylactides,polyvinyl esters, polyurethanes, cellulose esters, poly vinyl formal,poly vinyl butyral, polyethylene-co-vinyl acetate, and co-polymers ofany two or more thereof. Cross-linked films may further be produced bycross-linking such thermoplastic polymers.

Sealing Member

The sealing member is used to join the first substrate to the secondsubstrate. The sealing member may be an adhesive material applied to onesubstrate or the other, or a dual system adhesive where a firstcomponent is applied to one substrate and a second component is appliedto the other and the two components combine on contact to bond thesubstrates together. Illustrative adhesives include, but are not limitedto, those containing epoxies, urethanes, cyanoacrylates, acrylics,polyimides, polyamides, polysulfides, phenoxy resin, polyolefins andsilicones. The sealing member may include a thermal cure system such asa thermal cure epoxy or an ultraviolet light curable seal.

The sealing member may alternatively be a weld between the firstsubstrate and the second substrate. In other words, a melting andjoining of two plastic substrates to one another or using a thirdmaterial such as when using a hot-melt. Of course, care must be taken inapplication of the conductive materials on the surface of the substratessuch that shorting of the device does not occur. In some embodiments,the weld between the first and the second substrate is an ultrasonicweld. It should be noted that a combination of techniques could be usedto seal the device. For instance a portion of the seal could be formedby welding uncoated areas of the substrates together followed byapplying a sealing adhesive that is UV cure to areas of the substratethat are coated with a coating such as a metal mesh coating or ananowire coating.

The sealing member may be a heat seal film which attaches to first andsecond substrate at the edge of the first and second substrate aroundthe circumference of the device. Thus, the heat seal film covers an edgeof the front surface of the first substrate and extends to an edge ofthe rear surface of the second substrate. This sealing member provides abarrier for the electrochromic medium or film from moisture and oxygen.The heat seal films are typically multilayers consisting of an innersealant layer, middle core layer, and outer barrier layer which may ormay not include an aluminum foil layer. The film can be applied using aheat sealer to attach the film to the edge of the device. An example ofa heat seal film without a foil layer includes Torayfan® CBS2 fromToray, and an example of a metallized heat seal film is Torayfan® PWXSfrom Toray. Additionally, a pressure sensitive adhesive can be added tothe inner sealant layer to adhere the film at room temperature or toimprove adhesion during heat sealing. An example of a pressure sensitiveadhesive for this purpose is 8142KCL from 3M™.

In another aspect, any of the above electrochromic devices is providedfurther including an electrochromic film, in addition to, or instead of,the electrochromic medium. The electrochromic films may be polymer-basedfilms (as described herein) that incorporate one or more electrochromicspecies in addition to a thermoplastic polymer. The electrochromic filmmay include, in addition to the thermoplastic polymer, an anodicmaterial, a cathodic material, or both a cathodic material and an anodicmaterial. The films may also include other additives such asplasticizers, cross-linking agents, electrochromic buffers, ultravioletlight-absorbing species, electrolyte salts, stabilizers, and gel-formingmaterials.

Within the chamber, the first surface of the second substrate, thesecond surface of the first substrate, or both such surfaces may becoated with the polymer-based films incorporating one or moreelectrochromic species. As an illustration, the first surface of thesecond substrate may be coated with a polymer-basd electrochromic filmthat includes an anodic material and a thermoplastic polymer, asdescribed above. In such illustrations, the chamber may then include amedium that incorporates a cathodic material, or a cathodic material maybe coated on the second surface of the first substrate as either apolymer-based electrochromic film or as a metal oxide, such as tungstenoxide.

Electrochromic devices that include a thermoplastic electrochromic filmmay be formed of flexible substrates. For example, the flexiblesubstrates may be a flexible plastic substrate having a flexiblecoating. This will provide for the formation of flexible electrochromicdevice. In one embodiment, a first and a second flexible plasticsubstrate is coated with gas barrier layer and a conductive material. Adevice is prepared, such that a second surface of the first substrate isproximal to a first surface of a second substrate, with a sealing memberjoining the first substrate to the second substrate, and forming achamber therebetween. However, prior to joining the substrates, thesecond surface of the first substrate is coated with an electrochromicmaterial, such as a metal oxide like tungsten oxide, or a thermoplasticelectrochromic film, while the first surface of the second substrate iscoated with a metal oxide or thermoplastic electrochromic film.Alternatively, a thermoplastic electrochromic film incorporating acathodic material, an anodic material, a thermoplastic polymer, and asolvent may be formed and applied to substrate having a conductivesurface. The electrochromic device may then be formed by applying asecond substrate with a conductive surface and edge sealing the deviceto retain and protect the thermoplastic electrochromic film within achamber of the device. Edge sealing may include a polymeric adhesivesuch as an epoxy-containing material, or it may be a plastic weld, aheat seal film, a hot melt, a thermosetting material or a UV curingmaterial.

The devices thus described, methods or preparing such devices aredescribed. For example, devices having a polymer-based electrochromicfilm may be formed by assembling a first substrate, a second substrate,and the polymer-based electrochromic film disposed therebetween. Thiscan include mere assembly of the various parts, or complete assemblyfrom film fabrication to device manufacture.

In another aspect a process is provided forming a substrate for anelectrochromic device having a polymer film. The process may includecoating a first surface of a first substrate with a first polymer-basedelectrochromic film, the polymer-based electrochromic film having atleast one first electroactive material and a first thermoplasticpolymer. Illustrative coating techniques may include, but are notlimited to, slot-die coating, gravure coating, curtain coating, spraycoating, dip coating, extrusion coating, or slide coating. Suchprocesses should be amenable to a wide range of electrochromic materialsinclude the use of a viologen, a phenazine, a phenothiazine, atriphenodithiazine, a carbazole, an indolocarbazole, a biscarbazole, ora ferrocene. This may be repeated multiple times for multi-layerdevices, or for separate substrates, each containing a different type ofpolymer-based electrochromic films, where it is a cathodic, anodic, orboth cathodic and anodic species in the same film.

In another aspect, an electrochromic device includes a first substratehaving a first surface and a second surface; a second substrate having afirst surface and a second surface; and a sealing member, joining thesecond surface of the first substrate to the first surface of the secondsubstrate forming a chamber therebetween; wherein first substratecontains an ultraviolet light absorbing material; the second surface iscoated with a first polymer-based electrochromic film (as describedherein) comprising an anodic material; and the chamber comprises anfluid medium containing a UV-curable gelling agent. UV-curable gellingagents may include a polyfunctional vinyl compound or an oligomer suchas an acrylate, methacrylate, or vinyl ether, and a radicalphotoinitiator. Illustrative vinyl compounds include but are not limitedto, 1,4-butanediol diacrylate, tris[2-(acryloyloxy)ethyl] isocyanurate,poly(propylene glycol) diacrylate, poly(propylene glycol)dimethacrylate, poly(ethylene glycol) diacrylate, trimethylolpropanepropoxylate triacrylate and 1,4-butanediol divinyl ether, andcombinations thereof, to name a few. In addition to the polyfunctionalvinyl compounds, monomeric vinyl compounds may also be included into theUV-curable gel to help modify the final properties of the gel, likemethyl methacrylate or butyl acrylate, to name a few. The radicalphotoinitiator, which also would need to be incorporated, could be, butnot limited to, 2-Hydroxy-2-methylpropiophenone,2,2-dimethoxy-2-phenylacetophenone (Irgacure® 651),2,2-diethoxyacetophenone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure® 819).

In some embodiments, the fluid medium contains a cathodic material, asdescribed above. For example, the cathodic material may be a viologen.

In other embodiments, the fluid medium further may include anultraviolet light-absorbing material, an ultraviolet-curable gellingagent, or a mixture of any two or more thereof.

In some embodiments, the first surface of the second substrate is coatedwith a second polymer-based electrochromic film including a cathodicmaterial. In such embodiments, the cathodic material may be any of thoseas described above. In some embodiments, the cathodic material is aviologen.

The anodic material in such devices may be any of those as describedabove, including, but not limited to, a phenazine, a phenothiazine, atriphenodithiazine, a carbazole, an indolocarbazole, a biscarbazole, ora ferrocene.

In some embodiments, the first surface of the second substrate is coatedwith a metal oxide. For example, the metal oxide may be tungsten oxide.

The fluid medium in the device may include a solvent. In someembodiments, the fluid medium may also include an electrolytic salt.

In another aspect, a process of gelling a fluid medium in anelectrochromic device is provided where an electrochromic device isprovided, the device including a first substrate having a first surfacecomprising a ultraviolet absorbing layer, and a second surface; a secondsubstrate having a first surface and a second surface; and a sealingmember, joining the second surface of the first substrate to the firstsurface of the second substrate forming a chamber therebetween. Thechamber may include a fluid medium including an ultravioletlight-curable gelling agent, with the process further includingirradiating the ultraviolet light-curable gelling agent through thesecond substrate with ultraviolet light.

In such embodiments, the fluid medium may further include any of theabove cathodic materials, ultraviolet light-absorbing materials, or amixture thereof. In the process, the second surface of the firstsubstrate may include a first polymer-based electrochromic layerincluding an anodic material. Illustrative anodic materials are those asdescribed above, including but not limited to, a phenazine, aphenothiazine, a triphenodithiazine, a carbazole, an indolocarbazole, abiscarbazole, or a ferrocene. In the process, the first surface of thesecond substrate is coated with a second polymer-based electrochromicfilm including a cathodic material, as described above, or a metal oxidethat is cathodic.

In the process, also included may be a step of applying the sealingmember to either the first substrate or the second substrate andapplying the remaining substrate to the sealing member. The process mayalso include curing the sealing member.

In the process, the sealing member may include a thermal cure resin, anultraviolet light curable resin, or a combination thereof. Such resinsmay include, but are not limited to epoxy resins, cyanoacrylates,silicones, urethanes, polyimides, acrylate resins, and or methacrylateresins and combinations of any two or more thereof. Where the resin isUV curable, it may be cured by then irradiating the sealing member withultraviolet light through the second substrate, and where the resin isthermally curable, it may be cured by heating or exposing the resin toheat. Alternatively, the sealing member includes a weld between thefirst substrate and the second substrate, hot melting a third thermalplastic, or heat seal film.

In another aspect, an electrochromic device is provided. The device hasa first substrate having a front surface and a rear surface including aconductive nanowire or a conductive metal mesh. In the device, the frontsurface, the rear surface, or both the front surface and the rearsurface of the first substrate includes a gas diffusion barrier. Thedevice also has a second substrate including a front surface having aconductive nanowire or a conductive metal mesh. In the device, the frontsurface, the rear surface, or both the front surface and the rearsurface of the second substrate includes a gas diffusion barrier. In thedevice, the first substrate is joined to the second substrate by asealing member, where the rear surface of the first substrate and thefront surface of the second substrate with the sealing member define achamber therebetween and the first substrate is a plastic substrate.

In some embodiments, the second substrate is a plastic substrate and thefront surface, the rear surface, or both the front surface and the rearsurface of the second substrate comprises a gas diffusion barrier. Thechamber of the device may include an electrochromic medium having acathodic material, an anodic material, or both a cathodic and an anodicmaterial. In such embodiments, the electrochromic device is flexible orrigid having two plastic substrates that bend and flex.

The rear surface of the first substrate may include a conductivenanowire coating, a conductive metal mesh, or an IMI stack, and thefront surface of the second substrate may include a conductive nanowirecoating, a conductive metal mesh, or an IMI stack as well. The metalmesh materials and IMI stacks are as described above. In addition to themetal meshes, nanowire coatings, and IMI stacks, the rear surface of thefirst substrate and the front surface of the second substrate mayinclude a conductive coating disposed between the conductive nanowirecoating, conductive metal mesh, or IMI stack and the chamber.Alternatively, in addition to the metal meshes and IMI stacks, the rearsurface of the first substrate and the front surface of the secondsubstrate may include a conductive coating disposed between the nanowirecoating/conductive metal mesh/IMI stack and the chamber or between thenanowire coating/conductive metal mesh/IMI stack and the substrate.

Illustrative conductive coatings may include a thin metal layer, atransparent conductive metal oxide, carbon nanotubes, graphene, or aconductive polymer. For example, the conductive coating may include athin gold layer, a thin platinum group metal layer, indium tin oxide,indium zinc oxide, carbon nanotubes, graphene, orpoly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS). Insome embodiments, the conductive coating may include indium tin oxide.

In some embodiments, the first substrate may include a plasticsubstrate, the second substrate may be a plastic substrate, or both thefirst substrate and the second substrate are plastic. One or both of thefirst and second substrates may also be flexible or rigid.

As in other devices described herein, the sealing member of the devicemay include a UV-curable resin, a thermally curable resin, hot melt, aweld, or a heat seal film. Illustrative such sealing members aredescribed above.

As in any of the devices above, either or both of the first surface ofthe first substrate and the second surface of the second substrate mayinclude a scratch-resistant coating. The scratch resistant coatings maybe organic, inorganic, or combinations of both. Hard coatings may becomposed of organic resins only, hybrid coatings through bonding oforganic resins with inorganic particles, or composite coatings oforganic resins with inorganic fillers. The hard coats commonly used forplastic substrates are solvent based, UV curable acrylics with silicafillers. Illustrative scratch-resistant coatings include, but are notlimited to, Acier C50PG available from Nidek Company which is a hybridorganic/inorganic, UV curable, acrylic based hard coat. Inorganiccoatings applied by physical vapor deposition or chemical vapordeposition can be used to form a hard coat. These layers are typicallyin the range of 100 nm to 25 μm thick. A hard coat may use a combinationof a hard organic layer as a base coat followed by a much harderinorganic layer. A hard coat may also be where a diamond like carbon(DLC) layer is applied over the inorganic hard coat layer. The organiclayer is typically 25 to 1000 microns thick, the inorganic layer istypically 100 nm to 25 microns thick and the diamond like carbon layeris typically 1 to 100 nm thick.

The gas diffusion barrier(s) on the device may include, but is notlimited to, a layer applied by plasma-enhanced chemical vapor deposition(PECVD), a layer applied by neutral beam assisted sputtering (NBAS), alayer applied by atomic layer deposition (ALD), a poly(ethylene-co-vinylalcohol) (EVOH) coating, a polyvinyl alcohol (PVOH) coating, a polymericfilm of self-assembled nanoparticles (SNAP), multilayer barrier ofalternating thin films of cationic and anionic polymers deposited bylayer-by-layer deposition or a multilayer barrier comprising alternatinglayers of organic and inorganic materials, or a flexible, thin glassfilm.

Where the cathodic or anodic materials are sequestered within a polymermatrix, the polymer matrix may be solid polymer or gel polymer that isthermoplastic or crosslinked. For example, as illustrated by theexamples, the polymer may be an acrylate-based polymer that is dissolvedin a solvent which incorporates the anodic or cathodic material. Thissolution is then coated on the conductive surface of a substrate, wherethe solvent is then removed. The resultant film is an acrylate film thatmay be hard or tacky to the touch. Or, the polymer film maybe a gel thatcontains solvent as well as the anodic or cathode material. In addition,the polymer film maybe subsequently cross-linked for increasedmechanical stability. Other possible polymer matrix systems that couldbe used to sequester an anodic and cathodic materials: polyacrylate,polymethacrylates, polyethers, polyesters, polycarbonates andpolyurethanes, polysiloxanes, polysilanes, polyacrylonitriles,polystyrenes, polymethacrylonitriles, polyamides, polyimides,polyvinylidenehalides, polyvinyl butyral, and co-polymers orcombinations of any two or more thereof. Further examples of polymermatrix materials used in electrochromic devices can be found in U.S.Pat. Nos. 6,635,194 and 5,940,201.

As noted above, the anodic or cathodic materials may also be part of thepolymeric matrix with the anodic or cathodic material being covalentlybound to the polymer. This may be accomplished with the presence of afunctional group on the anodic or cathodic material that is reacted withthe polymer or monomers that make up the polymer. For example, where theanodic or cathodic materials contain a hydroxyl group, the anodic orcathodic material may be bound into a polymer matrix via a condensationreaction or react with an isocyanate functionality to form apolyurethane-based polymer matrix. Amines may also react with isocyanatefunctionalities to form urea and biuret linkages. It can be alsoanticipated that other cross-linked polymeric matrix can be formed usinga multifunctional epoxy or polymers in combination with a curing agentlike an amine, alcohol or anhydride or through base or acid catalyzedhomopolymerization.

Illustrative materials that may be used as the first and second polymermatrix materials include, but are polymethacrylates, polyacrylates,polystyrenes, polyurethanes, polyethers, polyesters, polycarbonates,polysiloxanes, polysilanes, polyacrylonitriles, polymethacrylonitriles,polyamides, polyimides, polyvinylidenehalides, polyvinyl butyral andco-polymer and combinations of thereof. Further examples of polymermatrix materials can be found in U.S. Pat. Nos. 6,635,194 and 5,940,201.

The electrolyte may include a solvent and a salt. The salt may be ametal salt or an ammonium salt. Illustrative solvents for use in theelectrolyte may include, but are not limited to, 3-methylsulfolane,dimethyl sulfoxide, dimethyl formamide, tetraglyme and other polyethers;alcohols such as ethoxyethanol; nitriles, such as acetonitrile,glutaronitrile, 3-hydroxypropionitrile, and 2-methylglutaronitrile;ketones including 2-acetylbutyrolactone, and cyclopentanone; cyclicesters including beta-propiolactone, gamma-butyrolactone, andgamma-valerolactone; carbonates including propylene carbonate (PC),ethylene carbonate, methy ethyl carbonate; and homogenous mixtures ofthe same. While specific solvents have been disclosed as beingassociated with the electrolyte, numerous other solvents that would beknown to those having ordinary skill in the art having the presentdisclosure before them are likewise contemplated for use. Illustrativesalts include, but are not limited to, metal or ammonium salts, such asbut not limited to Li⁺, Na⁺, K⁺, NR′₄, where each R′ is individually H,alkyl, or cycloalkyl, of the following anions F⁻, Cl⁻, Br⁻, I⁻, BF₄ ⁻,PF₆ ⁻, SbF₆ ⁻, AsF₆ ⁻, ClO₄ ⁻, SO₃CF₃ ⁻, N(CF₃SO₂)₂ ⁻, C(CF₃SO₂)₃ ⁻,N(SO₂C₂F₅), Al(OC(CF₃)₃)₄ ⁻, or BAr₄ ⁻, wherein Ar is a aryl orfluorinated aryl group such as, but not limited to, C₆H₅,3,5-(CF₃)₂C₆H₃, or C₆F₅.

The present invention, thus generally described, will be understood morereadily by reference to the following examples, which are provided byway of illustration and are not intended to be limiting of the presentinvention.

EXAMPLES Example 1: Electrochromic Gel Medium

An electrochromic medium was prepared from combining 38 mM ofN,N′-bis(n-octyl) viologen tetrafluoroborate; 27 mM of5,10-dihydro-5,10-dimethylphenazine; 15 mM of Tinuvin® 384-2 from BASF;50 mM of ethyl-2-cyano-3,3-diphenylacrylate; 0.5 mM of decamethylferrocene; 0.5 mM of decamethyl ferrocinium tetrafluoroborate; 2.2% byweight of a random copolymer made with 2-hydroxyethylmethacrylate andmethylarylate at a 1:10 molar ratio; 0.15% by weight of an isocyanatecrosslinker (Luprnate® MI from BASF), and about 0.3 to 2.0 parts permillion dibutyltin diacetate urethane catalyst in a propylene carbonatesolvent.

Example 2: Electrochromic Device Using Rigid Plastic Substrates withThermally Cured Seal

Rigid plastic substrates (approximately 50 mm wide, 125 mm long, 1.8 mmthick) were formed by injection molding of Zeonor 1420R. The secondsurface of the top plate and the first surface of the bottom plate werecoated with indium zinc oxide (IZO) at conditions appropriate for thepolymer substrate. An epoxy bead containing spacer beads was dispensedaround the perimeter of the bottom plate on top of the IZO coating. Asmall gap was left in the bead to act as a fill port after the seal iscured. The top plate was positioned with an offset to the bottom plateallowing access and electrical contact to the conductive coatings fromthe edges. The top plate was pressed down on the epoxy to the spacerbeads forming a cell. The epoxy seal was thermally cured at atemperature appropriate for the seal and polymer substrate. The cell wasfilled with the electrochromic gel medium of Example 1 and the fill portwas plugged using a UV curable epoxy. Busbars were applied to the offsetedges producing a rigid plastic electrochromic device with a thermallycured seal.

Example 3: Electrochromic Device Using Rigid Plastic Substrates with UVCured Seal

Same substrate preparation as Example 2. An epoxy bead containing spacerbeads was dispensed around the perimeter of the bottom plate on top ofthe IZO coating. A small gap was left in the bead to act as a fill portafter the seal is cured. The top plate was positioned with an offset tothe bottom plate allowing access and electrical contact to theconductive coatings from the edges. The top plate was pressed down onthe epoxy to the spacer beads forming a cell. The epoxy seal was UVcured at a time and intensity appropriate for the seal and polymersubstrate. The cell was filled with the electrochromic gel medium ofExample 1 and the fill port was plugged using a UV curable epoxy.Busbars were applied to the offset edges producing a rigid plasticelectrochromic device with a UV cured seal.

Example 4: Electrochromic Device Using Rigid Plastic Substrates with GasBarrier Coatings and a Thermally Cured Seal

Rigid plastic substrates (approximately 50 mm wide, 125 mm long, 1.8 mmthick) were formed by injection molding of Zeonor 1420R. The secondsurface of the top plate and the first surface of the bottom plate werecoated with gas barrier layer followed by indium zinc oxide (IZO) atconditions appropriate for the polymer substrate. An epoxy beadcontaining spacer beads was dispensed around the perimeter of the bottomplate on top of the IZO coating. A small gap was left in the bead to actas a fill port after the seal is cured. The top plate was positionedwith an offset to the bottom plate allowing access and electricalcontact to the conductive coatings from the edges. The top plate waspressed down on the epoxy to the spacer beads forming a cell. The epoxyseal was thermally cured at a temperature appropriate for the seal andpolymer substrate. The cell was filled with the electrochromic gelmedium of Example 1 and the fill port was plugged using a UV curableepoxy. Busbars were applied to the offset edges producing a rigidplastic electrochromic device with gas barrier coatings and a thermallycured seal. Illustrative gas barrier coatings may be applied as follows:SiO₂—sputtered single or double layer, accucoat SiO₂—low temperature PVDprocess, Excapsulix ALD—Atomic layer deposition of Al₂O₃,Gencoa—AlO_(x)/poly HMDSO multilayers, or PlasmaSi—PECVD SiN_(x)

Example 5: Electrochromic Device Using Rigid Plastic Substrates with GasBarrier Films and a Thermally Cured Seal

Rigid plastic substrates (approximately 50 mm wide, 125 mm long, 1.8 mmthick) were formed by injection molding of Zeonor 1420R. A gas barrierfilm was applied to the second surface of the top plate and the firstsurface of the bottom plate using UV curable liquid optically clearadhesives or barrier optically clear adhesives with the barrier layersorientated towards the plastic substrate and the PET carrier filmorientated to the outside. The exposed PET films were coated with indiumzinc oxide (IZO) at conditions appropriate for the polymer substrate. Anepoxy bead containing spacer beads was dispensed around the perimeter ofthe bottom plate on top of the IZO coating. A small gap was left in thebead to act as a fill port after the seal is cured. The top plate waspositioned with an offset to the bottom plate allowing access andelectrical contact to the conductive coatings from the edges. The topplate was pressed down on the epoxy to the spacer beads forming a cell.The epoxy seal was thermally cured at a temperature appropriate for theseal and polymer substrate. The cell was filled with the electrochromicgel medium of Example 1 and the fill port was plugged using a UV curableepoxy. Busbars were applied to the offset edges producing a rigidplastic electrochromic device with gas barrier films and a thermallycured seal. Illustrative gas barrier films include Kuraray EVAL—EvOHfilm (ethylene vinyl alcohol), Kuraray Exceval—PvOH film (propylenevinyl alcohol), Fujifilm—Transparent Super Gas Barrier film, and3M—FTB3-125 Barrier film.

Example 6: Electrochromic Device Using Flexible Plastic Substrates withGas Barrier Films, Metal Mesh Conductors and a UV Cured Seal

Flexible gas barrier films (approximately 75 mm wide, 82 mm long, 125microns thick) were cut from stock. Flexible metal mesh conductor films(approximately 75 mm wide, 82 mm long, 125 microns thick) overcoatedwith cold ITO were cut from stock. The metal mesh films were applied tothe second surface of the top gas barrier film and the first surface ofthe bottom gas barrier film using UV curable liquid optically clearadhesives or barrier optically clear adhesives with the barrier layersorientated towards the plastic substrate and the PET carrier filmorientated to the outside. A conductive silver ink trace was applied tothe offset edge of the assembled films and thermally cured. The silverink trace will act as a busbar when the device is assembled. An epoxybead containing spacer beads was dispensed around the perimeter of thebottom substrate on top of the ITO overcoated metal mesh. A small gapwas left in the bead to act as a fill port after the seal is cured. Thetop substrate was positioned with an offset to the bottom substrateallowing access and electrical contact to the silver ink on the edges.The top substrate was pressed down on the epoxy to the spacer beadsforming a cell. The epoxy seal was UV cured at a time and intensityappropriate for the seal and polymer substrate. The cell was filled withthe electrochromic gel medium of Example 1 and the fill port was pluggedusing a UV curable epoxy. Electrical connections were applied to theoffset edges producing a flexible plastic electrochromic device with gasbarrier films, metal mesh conductors and a UV thermally cured seal. Themetal mesh film used was Applied Nanotech, Inc, Exclucent™ coppermetallic and the gas barrier film was 3M FTB3-125 Barrier film.

Example 7: Electrochromic Device Using Glass Clad Rigid PlasticSubstrates with Thermally Cured Seal

Rigid plastic substrates (approximately 100 mm wide, 100 mm long, 2.0 mmthick) were cut from polycarbonate sheet. The polycarbonate substrateswere clad on one side with 0.3 mm soda lime glass which was coated withindium zinc oxide (IZO). The glass cladding was adhered to the plasticsubstrate using UV curable liquid optically clear adhesives or waslaminated using thermoplastic or thermoset optical interlayers with theIZO coating facing outward. An epoxy containing spacer beads wasdispensed around the perimeter of the bottom substrate on top of the IZOcoating. A small gap was left in the bead to act as a fill port afterthe seal is cured. The top substrate was positioned with an offset tothe bottom substrate allowing access and electrical contact to theconductive coatings from the edges. The top substrate, with the IZOcoating orientated towards the bottom substrate IZO coating, was presseddown on the epoxy to the spacer beads forming a cell. The epoxy seal wasthermally cured at a temperature appropriate for the seal and polymersubstrate. The cell was filled with electrochromic fluid and the fillport was plugged using a UV curable epoxy. Busbars were applied to theoffset edges producing a glass clad, rigid plastic electrochromic devicewith a thermally cured seal.

Example 8

Representative plastic devices of the present technology were put into aOxygen Autoclave chamber (400 psi) and their optical properties weremeasured regularly with a UV/Vis spectrometer. The absorbance at 461 nmwas attributed to oxygen contamination of the electrochromic medium andwas monitored and compared to reference parts (01 Glass/IZO, and 02Zeonor/IZO). The plastic device without a gas barrier coating representsthe highest absorbance change over time. FIG. 4 shows the results ofoxygen testing performance for various gas barrier materials. A plasticdevice with no barrier [02_Zeonor/IZO(−18)] shows an absorbance changegreater than 0.1 units after 3 days exposure. A plastic device with SiO₂and Al₂O₃ deposited by ALD [21-2B-02_100nmSiO₂/50 nm ALD-Al₂O₃/IZO]shows better stability and did not pass the 0.1 absorbance unit increasethreshold until the 8 day point. For devices comprising EVOH[04_EVOH(−35)] and SiO₂ [16_SiO₂ 100 nm/100 nm(−102)] gas barriers, the0.1 unit absorbance change threshold occurred after 9 days. Furthermore,a 100 nm SiO₂ layer coated on both side of the plastic substrates[21-1C-01_100SiO₂/Zeo/100nmSiO₂/25 nm ALD-Al₂O₃/IZO] performed almost 5times better than a plastic device without a barrier. Based on FIG. 4, adevice with a AlO_(x)/poly-acrylate multilayer barrier[P232-3_1_AlO_(x)/poly-acrylate multilayers(−R302)] obtained similarperformance to the no barrier [02_Zeonor/IZO(−18)] plastic device in theOxygen autoclave test reaching 0.1 units of absorbance change after 3days of testing. However, the speed of degradation beyond 3 days isslower than the no barrier device. Thus, all plastic devices with gasbarriers showed significantly slower rates of degradation than deviceswith no gas barrier.

Example 9

An electrochromic device with flexible plastic substrates wasconstructed. An indium tin oxide (ITO) coated piece of 8″×10″ PET (6 milthickness; 120 Ω/sq sheet resistance) was coated with a mixture made bydissolving 1.02 grams of bis (11-hydroxyundecyl) viologenbis[bistrifluoromethanesulfonyl imide] (NTf) and 0.38 grams of HDT(hexamethylene diisocyanate trimer purchased from Sigma-Aldrich) in 7.0grams of a solvent mixture (“SM1”), plus 117 microliters of a 0.6 wt %solution of dibutyltin diacetate (DBTDA) catalyst in SM1, therebyforming a first film. This coating was made using a #10 Mayer rod tocontrol thickness. A second piece of 8″×10″ PET was coated with asolution made by dissolving 1.02 grams of bis [5, 10-(4-(3-hydroxypropyldimethylammonium) butyl]-5, 10-dihydrophenazine NTf and 0.38 grams ofHDT in 7.0 grams of SM1 and 117 microliters of DBTDA in SM1 therebyforming a second film. This film was also made with a #10 Mayer rod. Thefilms were allowed to cure under a nitrogen atmosphere overnight in anoven at 60° C. A third coating was prepared by combining 15 gramsVinylec H (SPI Supplies), 15 grams Vinylec E (SPI Supplies), 1.6 gramstetramethylammonium tetrafluoroborate, and 88 grams propylene carbonateand heating (120° C.) under nitrogen with mechanical stirring forming arelatively high viscosity solution that was then applied between tworelease liners (3M 4935). The release liners and fluid were fed throughthe nip on a manual extruder to deliver a 250 micron coating. Thecoating was then allowed to cool to ambient temperature and maintainedunder nitrogen until use. 3.5″×3.5″ squares of the first and secondcoatings were cut and the EC coating removed along one edge usingmethanol and a cotton swab and electrical contact made to the ITO via 3Madhesive strip 3011. A section of the third coating slightly larger than3.5″×3.5″ was cut and applied to the first coating so that the entiresurface of the first coating was covered by the third coating. Thesecond coating which was then applied to the exposed surface of thethird coating such that the electrical contacts to the first and secondcoatings were on opposite sides of the element. The element was thenplaced between two pieces of glass (2.2 mm, 5″×5″ each) and placed underreduced pressure for 30 minutes to remove bubbles at the coatinginterfaces, after which the element was returned to ambient pressure viaa slow nitrogen bleed. An epoxy seal was placed around the perimeter andelectrical contacts, and subsequently cured at ambient temperatureovernight to complete the element.

Illustrative Embodiments

Following is a description of non-limiting illustrative embodiments.

Para. A. An electrochromic device comprising: a first flexible or rigidplastic substrate comprising: a front surface; and a rear surface;wherein: the rear surface comprises a first conductive material; and thefront surface, the rear surface, or both the front surface and the rearsurface of the first substrate comprises a gas diffusion barrier; asecond flexible or rigid plastic substrate comprising: a front surface;and a rear surface; wherein: the front surface comprises a secondconductive material; wherein: the first substrate is joined to thesecond substrate by a sealing member, where the rear surface of thefirst substrate and the front surface of the second substrate with thesealing member define a chamber therebetween.

Para. B. The electrochromic device of Para. A, wherein the frontsurface, the rear surface, or both the front surface and the rearsurface of the second substrate comprises a gas diffusion barrier; andoptionally wherein the front surface, the rear surface, or both thefront surface and the rear surface of the first and second substratescomprises an adhesion promotion layer.

Para. C. The electrochromic device of Para. A or B, wherein the chambercomprises an electrochromic medium comprising a cathodic material and ananodic material.

Para. D. The electrochromic device of any one of Paras. A-C, wherein thegas diffusion barrier(s) comprises a layer applied by plasma-enhancedchemical vapor deposition (PECVD), a layer applied by neutral beamassisted sputtering (NBAS), a layer applied by atomic layer deposition(ALD), a co-polymer of ethylene vinyl alcohol, a polyvinyl alcohol, apolymeric film of self-assembled nanoparticles (SNAP), a multilayerbarrier comprising alternating layers of organic and inorganicmaterials, a multilayer barrier comprising alternating thin films ofcationic and anionic polymers, or a flexible, thin glass film adhered orlaminated to the substrate.

Para. E. The electrochromic device of any one of Paras. A-D, wherein thefirst substrate, the second substrate, or both the first substrate andthe second substrate comprise polyethylene naphthalate (PEN),polyacrylonitrile, polyethylene terephthalate (PET), polycarbonate, acycloolefin polymer (COP), a cycloolefin co-polymer (COC), an acrylic, apolyamide, or an epoxy.

Para. F. The electrochromic device of any one of Paras. A-E, wherein thefirst conductive material comprises a conductive nanowire coating, aconductive metal mesh, or an IMI stack.

Para. G. The electrochromic device of any one of Paras. A-F, whereinsecond conductive material comprises a conductive nanowire coating, aconductive metal mesh, an insulator/metal/insulator stack (IMI stack), atransparent polymer filled with nanoparticles (such as indium tin oxideparticles), carbon nanotubes, graphene, or a conductive polymer.

Para. H. The electrochromic device of any one of Paras. A-G, wherein thefirst conductive material comprises a first conductive nanowire coating,a first conductive metal mesh, or a first IMI stack; and the secondconductive material comprises a second conductive nanowire coating, asecond conductive metal mesh, or a second IMI stack, a secondtransparent polymer filled with nanoparticles (such as indium tin oxideparticles), carbon nanotubes, graphene, or a second conductive polymer.

Para. I. The electrochromic device of any one of Paras. A-H, wherein theconductive nanowire coating, the conductive metal mesh, IMI stack,transparent polymer filled with nanoparticles, carbon nanotubes,graphene, or conductive polymer exhibits a resistance of less than 50Ω/sq.

Para. J. The electrochromic device of any one of Paras. A-I, wherein theconductive nanowire coating, the conductive metal mesh, IMI stack,transparent polymer filled with nanoparticles, carbon nanotubes,graphene, or conductive polymer exhibits a resistance of less than 10Ω/sq, or less than 5 Ω/sq.

Para. K. The electrochromic device of any one of Paras. A-J furthercomprising a conductive coating overlaying either or both of the firstor second conductive material.

Para. L. The electrochromic device of Para. K, wherein the conductivecoating comprises a transparent conductive oxide, carbon nanotubes,graphene, or a conductive polymer.

Para. M. The electrochromic device of Para. K or L, wherein theconductive coating comprises indium tin oxide, indium zinc oxide, carbonnanotubes, graphene, or poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT-PSS).

Para. N. The electrochromic device of Para. M, wherein the conductivecoating comprises indium tin oxide or indium zinc oxide.

Para. O. The electrochromic device of any one of Paras. A-N, wherein thesealing member comprises a thermally-curable seal or anultraviolet-curable seal.

Para. P. The electrochromic device of any one of Paras. A-O, wherein thesealing member comprises an epoxy.

Para. Q. The electrochromic device of any one of Paras. A-P, wherein thesealing member comprises a weld between the first substrate and thesecond substrate.

Para. R. The electrochromic device of any one of Paras. A-Q, wherein thesealing member comprises a hot melt or an ultrasonic weld between thefirst substrate and the second substrate, or a heat seal film thatcovers an edge of the front surface of the first substrate and extendsto an edge of the rear surface of the second substrate.

Para. S. The electrochromic device of any one of Paras. A-R, wherein thechamber comprises a first polymer-based electrochromic film, preferablya first thermoplastic electrochromic film.

Para. T. The electrochromic device of Para. S, wherein the firstpolymer-based electrochromic film comprises a first electroactivematerial and a first thermoplastic polymer.

Para. U. The electrochromic device of Para. S or T, wherein the firstelectroactive material is a cathodic material, and anodic material, or amixture of a cathodic material and an anodic material.

Para. V. The electrochromic device of Para. U, wherein the cathodicmaterial comprises a viologen.

Para. W. The electrochromic device of Para. U or V, wherein the anodicmaterial comprises a phenazine, a phenothiazine, a triphenodithiazine, acarbazole, an indolocarbazole, a biscarbazole, or a ferrocene.

Para. X. The electrochromic device of any one of Paras. S-W, wherein thefirst polymer-based electrochromic film comprises a plasticizer.

Para. Y. The electrochromic device of any one of Paras. S-X, wherein thefirst polymer-based electrochromic film is a cross-linked film.

Para. Z. The electrochromic device of any one of Paras. S-Y, wherein thechamber comprises a second polymer-based electrochromic film comprisinga second electroactive material and a second thermoplastic polymer,preferably where the second polymer-based electrochromic film is athermoplastic electrochromic film.

Para. AA. The electrochromic device of Para. Z, wherein the first andsecond polymer-based electrochromic films are separated by anion-exchange or porous membrane, preferably where the first and secondpolymer-based electrochromic films are each independently thermoplasticelectrochromic films.

Para. AB. A process of forming a substrate for an electrochromic device,the process comprising coating a first surface of a first flexible orrigid plastic substrate with a first polymer-based film, thepolymer-based electrochromic film comprising at least one firstelectroactive material and a first thermoplastic polymer, the firstsurface further comprising a conductive nanowire coating, a conductivemetal mesh, or an IMI stack, and a gas barrier coating on a secondsurface of the first flexible or rigid plastic substrate, the secondsurface being substantially parallel to and opposite from the firstsurface.

Para. AC. The process of Para. AB, wherein the coating comprises slotdie coating, gravure coating, curtain coating, spray coating, dipcoating, extrusion coating, or slide coating.

Para. AD. The process of Para. AB or AC further comprising joining thefirst surface of the first substrate comprising the first polymer-basedelectrochromic film (preferably a thermoplastic electrochromic film) toa first surface of a second substrate with a sealing member, and forminga chamber therebetween.

Para. AE. The process of Para. AD further comprising coating the firstsurface of the second substrate with a second polymer-basedelectrochromic film (preferably a thermoplastic electrochromic film),the second electrochromic film comprising at least one secondelectroactive material and a second thermoplastic polymer.

Para. AF. The process of any one of Paras. AB-AE, wherein the firstelectroactive material is a cathodic material.

Para. AG. The process of any one of Paras. AB-AF, wherein the firstelectroactive material is an anodic material.

Para. AH. The process of any one of Paras. AE-AG, wherein the secondelectroactive material is a cathodic material.

Para. AI. The process of Para. AH, wherein the second electroactivematerial is an anodic material.

Para. AJ. The process of any one of Paras. AE-AI, wherein the firstelectroactive material is a cathodic material and the secondelectroactive material is an anodic material.

Para. AK. The process of any one of Paras. AE-AI, wherein the firstelectroactive material is an anodic material and the secondelectroactive material is a cathodic material.

Para. AL. The process of any one of Paras. AD-AK further comprisingfilling the chamber with a fluid medium.

Para. AM. An electrochromic device comprising: a first flexible or rigidplastic substrate having a first surface and a second surface; a secondflexible or rigid plastic substrate having a first surface and a secondsurface; and a sealing member, joining the second surface of the firstsubstrate to the first surface of the second substrate forming a chambertherebetween; wherein: the first surface of the first substrate iscoated with an ultraviolet light absorbing layer; the second surface iscoated with a first polymer-based electrochromic film comprising ananodic material; and the chamber comprises an fluid medium containing aUV-curable gelling agent. The first polymer-based electrochromic film ispreferably a thermoplastic electrochromic film.

Para. AN. The electrochromic device of Para. AM, wherein the fluidmedium further comprises a cathodic material.

Para. AO. The electrochromic device of Para. AM or AN, wherein thecathodic material is a viologen.

Para. AP. The electrochromic device of any one of Paras. AM-AO, whereinthe fluid medium further comprises an ultraviolet absorbing material.

Para. AQ. The electrochromic device of any one of Paras. AM-AP, whereinthe first surface of the second substrate is coated with a secondpolymer-based electrochromic film comprising a cathodic material,preferably where the second polymer-based electrochromic film is athermoplastic electrochromic film.

Para. AR. The electrochromic device of Para. AQ, wherein the cathodicmaterial is a viologen.

Para. AS. The electrochromic device of any one of Paras. AM-AR, whereinthe anodic material is a phenazine, a phenothiazine, atriphenodithiazine, a carbazole, an indolocarbazole, a biscarbazole, ora ferrocene.

Para. AT. The electrochromic device of any one of Paras. AM-AS, whereinthe first surface of the second substrate is coated with a metal oxide.

Para. AU. The electrochromic device of Para. AT, wherein the metal oxideis tungsten oxide.

Para. AV. The electrochromic device of any one of Paras. AM-AU, whereinthe sealing member comprises a UV-curable resin or a thermal cure resin.

Para. AW. The electrochromic device of any one of Paras. AM-AV, whereinthe sealing member comprises a weld between the first substrate and thesecond substrate.

Para. AX. An electrochromic device comprising: a first flexible or rigidplastic substrate comprising: a front surface; and a rear surfacecomprising a conductive nanowire coating, a conductive metal mesh, or anIMI stack; wherein: the front surface, the rear surface, or both thefront surface and the rear surface of the first substrate comprises agas diffusion barrier; a second flexible or rigid plastic substratecomprising: a front surface comprising a conductive nanowire coating, aconductive metal mesh, or an IMI stack; and a rear surface; wherein: thefirst substrate is joined to the second substrate by a sealing member,wherein the rear surface of the first substrate and the front surface ofthe second substrate with the sealing member define a chambertherebetween.

Para. AY. The electrochromic device of Para. AX, wherein the secondsubstrate is a plastic substrate and the front surface, the rearsurface, or both the front surface and the rear surface of the secondsubstrate comprises a gas diffusion barrier.

Para. AZ. The electrochromic device of Para. AX or AY, wherein thechamber comprises an electrochromic medium comprising a cathodicmaterial and an anodic material.

Para. BA. The electrochromic device of any one of Paras. AX-AZ, whereinthe rear surface of the first substrate comprises the conductive metalmesh; and the front surface of the second substrate comprises theconductive metal mesh.

Para. BB. The electrochromic device of any one of Paras. AX-BA, whereinthe conductive nanowire coating, the conductive metal mesh, or the IMIstack exhibits a resistance of less than 50 Ω/sq.

Para. BC. The electrochromic device of any one of Paras. AX-BB, whereinrear surface of the first substrate and the front surface of the secondsubstrate each comprise a conductive coating disposed between theconductive nanowire coating, the conductive metal mesh, or the IMIstack, and the chamber.

Para. BD. The electrochromic device of Para. BC, wherein the conductivecoating comprises a transparent conductive oxide, carbon nanotubes,graphene, or a conductive polymer.

Para. BE. The electrochromic device of any one of Paras. AX-BD, whereinthe first surface of the first substrate and the second surface of thesecond substrate comprise a scratch-resistant coating.

Para. BF. The electrochromic device of Para. BE, wherein thescratch-resistant coating comprises Acier C50PG.

Para. BG. The electrochromic device of any one of Paras. AX-BF, whereinthe gas diffusion barrier(s) comprises a layer applied byplasma-enhanced chemical vapor deposition (PECVD), a layer applied byneutral beam assisted sputtering (NBAS), a layer applied by atomic layerdeposition (ALD), a co-polymer of ethylene vinyl alcohol, a polyvinylalcohol, a polymeric film of self-assembled nanoparticles (SNAP), or amultilayer barrier comprising alternating layers of organic andinorganic materials, or a multilayer barrier comprising of alternatingthin film of cationic and anionic polymers, or a flexible, thin glassfilm.

Para. BG. An electrochromic device comprising: a flexible substratecomprising: a front surface; and a rear surface; wherein: the rearsurface comprises a first conductive material; and the front surface,the rear surface, or both the front surface and the rear surface of thefirst substrate comprises a gas diffusion barrier; a rigid substratecomprising: a front surface; and a rear surface; wherein: the frontsurface comprises a second conductive material; wherein: the flexiblesubstrate is shape conforming to the rigid substrate; and the flexiblesubstrate is joined to the rigid substrate by a sealing member, wherethe rear surface of the flexible substrate and the front surface of therigid substrate with the sealing member define a chamber therebetween.

Para. BH. The electrochromic device of Para. BG, wherein the frontsurface, the rear surface, or both the front surface and the rearsurface of the rigid or flexible substrate comprises a gas diffusionbarrier.

Para. BI. The electrochromic device of Para. BG or BH, wherein thechamber comprises an electrochromic medium comprising a cathodicmaterial and an anodic material.

Para. BJ. The electrochromic device of any one of Paras. BG-BI, whereinthe gas diffusion barrier(s) comprises a layer applied byplasma-enhanced chemical vapor deposition (PECVD), a layer applied byneutral beam assisted sputtering (NBAS), a layer applied by atomic layerdeposition (ALD), a co-polymer of ethylene vinyl alcohol, a polyvinylalcohol, a polymeric film of self-assembled nanoparticles (SNAP), amultilayer barrier comprising alternating layers of organic andinorganic materials, or a multilayer barrier comprising alternating thinfilms of cationic and anionic polymers.

Para. BK. The electrochromic device of any one of Paras. BG-BJ, whereinthe flexible substrate, rigid substrate, or both the flexible substrateand the rigid substrate comprise polyethylene naphthalate (PEN),polyacrylonitrile, polyethylene terephthalate (PET), polycarbonate, acycloolefin polymer (COP), a cycloolefin co-polymer (COC), an acrylic, apolyamide, or an epoxy.

Para. BL. The electrochromic device of any one of Paras. BG-BK, whereinthe first conductive material comprises a conductive nanowire coating, aconductive metal mesh, or an IMI stack.

Para. BM. The electrochromic device of any one of Paras. BG-BL, whereinsecond conductive material comprises a conductive nanowire coating, aconductive metal mesh, or an IMI stack.

Para. BN. The electrochromic device of any one of Paras. BG-BM, whereinthe first conductive material comprises a first conductive metal mesh;and the second conductive material comprises a second conductive metalmesh.

Para. BO. The electrochromic device of any one of Paras. BG-BN, whereinthe conductive nanowire coating, the conductive metal mesh, or the IMIstack exhibits a resistance of less than 50 Ω/sq, or less than 10 Ω/sq,or less than 5 Ω/sq.

Para. BP. The electrochromic device of any one of Paras. BG-BO furthercomprising a conductive coating overlaying either or both of the firstor second conductive material.

Para. BQ. The electrochromic device of Para. BP, wherein the conductivecoating comprises a transparent conductive oxide, carbon nanotubes,graphene, or a conductive polymer.

Para. BR. The electrochromic device of Para. BQ, wherein the conductivecoating comprises indium tin oxide, indium zinc oxide, carbon nanotubes,graphene, or poly(3,4-ethylenedioxythiophene) polystyrene sulfonate(PEDOT-PSS).

Para. BS. The electrochromic device of Para. BR, wherein the conductivecoating comprises indium tin oxide or indium zinc oxide.

Para. BT. The electrochromic device of any one of Paras. BG-BS, whereinthe sealing member comprises a thermally-curable seal or anultraviolet-curable seal.

Para. BU. The electrochromic device of any one of Paras. BG-BT, whereinthe sealing member comprises an epoxy.

Para. BV. The electrochromic device of any one of Paras. BG-BU, whereinthe sealing member comprises a weld between the first substrate and thesecond substrate.

Para. BW. The electrochromic device of any one of Paras. BG-BV, whereinthe sealing member comprises a hot melt or an ultrasonic weld betweenthe first substrate and the second substrate, or a heat seal film thatcovers an edge of the front surface of the first substrate and extendsto an edge of the rear surface of the second substrate.

Para. BX. The electrochromic device of any one of Paras. BG-BW, whereinthe chamber comprises a first polymer-based electrochromic film,preferably a first thermoplastic electrochromic film.

Para. BY. The electrochromic device of Para. BX, wherein the firstpolymer-based electrochromic film comprises a first electroactivematerial and a first thermoplastic polymer.

Para. BZ. The electrochromic device of Para. BY, wherein the firstelectroactive material is a cathodic material, and anodic material, or amixture of a cathodic material and an anodic material.

Para. CA. The electrochromic device of Para. BZ, wherein the cathodicmaterial comprises a viologen.

Para. CB. The electrochromic device of Para. BZ or CA, wherein theanodic material comprises a phenazine, a phenothiazine, atriphenodithiazine, a carbazole, an indolocarbazole, a biscarbazole, ora ferrocene.

Para. CC. The electrochromic device of any one of Paras. BX-CB, whereinthe first polymer-based electrochromic film comprises a plasticizer.

Para. CD. The electrochromic device of any one of Paras. BX-CC, whereinthe first polymer-based electrochromic film is a cross-linked film.

Para. CE. The electrochromic device of any one of Paras. BX-CD, whereinthe chamber comprises a second polymer-based electrochromic filmcomprising a second electroactive material and a second thermoplasticpolymer, preferably where the second polymer-based electrochromic filmis a thermoplastic electrochromic film.

Para. CF. The electrochromic device of Para. CE, wherein the first andsecond polymer-based electrochromic films are separated by anion-exchange or porous membrane, preferably where the first and secondpolymer-based electrochromic films are independently thermoplasticelectrochromic films.

Para. CG. An electrochromic device comprising: a rigid substratecomprising: a front surface; and a rear surface; wherein: the rearsurface comprises a first conductive material; and the front surface,the rear surface, or both the front surface and the rear surface of thefirst substrate comprises a gas diffusion barrier; a flexible substratecomprising: a front surface; and a rear surface; wherein: the frontsurface comprises a second conductive material; wherein: the flexiblesubstrate is shape conforming to the rigid substrate; and the flexiblesubstrate is joined to the rigid substrate by a sealing member, wherethe rear surface of the flexible substrate and the front surface of therigid substrate with the sealing member define a chamber therebetween.

Para. CH. The electrochromic device of Para. CG, wherein the frontsurface, the rear surface, or both the front surface and the rearsurface of the rigid or flexible substrate comprises a gas diffusionbarrier.

Para. CI. The electrochromic device of Para. CG or CH, wherein thechamber comprises an electrochromic medium comprising a cathodicmaterial and an anodic material.

Para. CJ. The electrochromic device of any one of Paras. CG-CI, whereinthe gas diffusion barrier(s) comprises a layer applied byplasma-enhanced chemical vapor deposition (PECVD), a layer applied byneutral beam assisted sputtering (NBAS), a layer applied by atomic layerdeposition (ALD), a co-polymer of ethylene vinyl alcohol, a polyvinylalcohol, a polymeric film of self-assembled nanoparticles (SNAP), amultilayer barrier comprising alternating layers of organic andinorganic materials, or a multilayer barrier comprising alternating thinfilms of cationic and anionic polymers.

Para. CK. The electrochromic device of any one of Paras. CG-CJ, whereinthe flexible substrate, rigid substrate, or both the flexible substrateand the rigid substrate comprise polyethylene naphthalate (PEN),polyacrylonitrile, polyethylene terephthalate (PET), polycarbonate, acycloolefin polymer (COP), a cycloolefin co-polymer (COC), an acrylic, apolyamide, or an epoxy.

Para. CL. The electrochromic device of any one of Paras. CG-CL, whereinthe first conductive material comprises a conductive nanowire coating, aconductive metal mesh, or an IMI stack.

Para. CM. The electrochromic device of any one of Paras. CG-CL, whereinsecond conductive material comprises a conductive nanowire coating, aconductive metal mesh, or an IMI stack.

Para. CN. The electrochromic device of any one of Paras. CG-CM, whereinthe first conductive material comprises a first conductive nanowirecoating, a first conductive metal mesh, or a first IMI stack; and thesecond conductive material comprises a second conductive nanowirecoating, the second conductive metal mesh, or the second IMI stack.

Para. CO. The electrochromic device of any one of Paras. CG-CN, whereinthe conductive nanowire coating, the conductive metal mesh, or the IMIstack exhibits a resistance of than 50 Ω/sq, or less than 10 Ω/sq, orless than 5 Ω/sq.

Para. CP. The electrochromic device of any one of Paras. CG-CO furthercomprising a conductive coating overlaying either or both of the firstor second conductive material.

Para. CQ. The electrochromic device of Para. CP, wherein the conductivecoating comprises a transparent conductive oxide, carbon nanotubes,graphene, or a conductive polymer.

Para. CR. The electrochromic device of Para. CQ, wherein the conductivecoating comprises indium tin oxide, indium zinc oxide, carbon nanotubes,graphene, or poly(3,4-ethylenedioxythiophene) polystyrene sulfonate(PEDOT-PSS).

Para. CS. The electrochromic device of Para. CR, wherein the conductivecoating comprises indium tin oxide or indium zinc oxide.

Para. CT. The electrochromic device of any one of Paras. CG-CS, whereinthe sealing member comprises a thermally-curable seal or anultraviolet-curable seal.

Para. CU. The electrochromic device of any one of Paras. CG-CT, whereinthe sealing member comprises an epoxy.

Para. CV. The electrochromic device of any one of Paras. CG-CS, whereinthe sealing member comprises a weld between the first substrate and thesecond substrate.

Para. CW. The electrochromic device of any one of Paras. CG-CS, whereinthe sealing member comprises a hot melt or an ultrasonic weld betweenthe first substrate and the second substrate, or a heat seal film thatcovers an edge of the front surface of the first substrate and extendsto an edge of the rear surface of the second substrate.

Para. CX. The electrochromic device of any one of Paras. CG-CW, whereinthe chamber comprises a first polymer-based electrochromic film,preferably a thermoplastic electrochromic film.

Para. CY. The electrochromic device of Para. CX, wherein the firstpolymer-based electrochromic film comprises a first electroactivematerial and a first thermoplastic polymer.

Para. CZ. The electrochromic device of Para. CX or CY, wherein the firstelectroactive material is a cathodic material, and anodic material, or amixture of a cathodic material and an anodic material.

Para. DA. The electrochromic device of Para. CZ, wherein the cathodicmaterial comprises a viologen.

Para. DB. The electrochromic device of Para. CZ or DA, wherein theanodic material comprises a phenazine, a phenothiazine, atriphenodithiazine, a carbazole, an indolocarbazole, a biscarbazole, ora ferrocene.

Para. DC. The electrochromic device of Para. 108, wherein the firstpolymer-based electrochromic film comprises a plasticizer.

Para. DD. The electrochromic device of any one of Paras. CX-DC, whereinthe first polymer-based electrochromic film is a cross-linked film.

Para. DE. The electrochromic device of any one of Paras. CX-DD, whereinthe chamber comprises a second polymer-based electrochromic filmcomprising a second electroactive material and a second thermoplasticpolymer, preferably where the second polymer-based electrochromic filmis a thermoplastic electrochromic film.

Para. DF. The electrochromic device of Para. DE, wherein the first andsecond polymer-based electrochromic films are separated by anion-exchange or porous membrane, preferably where the first and secondpolymer-based electrochromic films are each independently thermoplasticelectrochromic films.

Para. DG. The electrochromic device of any one of Paras. A-AA and AM-DF,wherein the front surface, the rear surface, or both the front surfaceand the rear surface of the first and second substrates comprises anadhesion promotion layer.

While certain embodiments have been illustrated and described, it shouldbe understood that changes and modifications can be made therein inaccordance with ordinary skill in the art without departing from thetechnology in its broader aspects as defined in the following claims.

The embodiments, illustratively described herein may suitably bepracticed in the absence of any element or elements, limitation orlimitations, not specifically disclosed herein. Thus, for example, theterms “comprising,” “including,” “containing,” etc. shall be readexpansively and without limitation. Additionally, the terms andexpressions employed herein have been used as terms of description andnot of limitation, and there is no intention in the use of such termsand expressions of excluding any equivalents of the features shown anddescribed or portions thereof, but it is recognized that variousmodifications are possible within the scope of the claimed technology.Additionally, the phrase “consisting essentially of” will be understoodto include those elements specifically recited and those additionalelements that do not materially affect the basic and novelcharacteristics of the claimed technology. The phrase “consisting of”excludes any element not specified.

The present disclosure is not to be limited in terms of the particularembodiments described in this application. Many modifications andvariations can be made without departing from its spirit and scope, aswill be apparent to those skilled in the art. Functionally equivalentmethods and compositions within the scope of the disclosure, in additionto those enumerated herein, will be apparent to those skilled in the artfrom the foregoing descriptions. Such modifications and variations areintended to fall within the scope of the appended claims. The presentdisclosure is to be limited only by the terms of the appended claims,along with the full scope of equivalents to which such claims areentitled. It is to be understood that this disclosure is not limited toparticular methods, reagents, compounds compositions or biologicalsystems, which can of course vary. It is also to be understood that theterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting.

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, particularly in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” “greater than,” “less than,” and the like,include the number recited and refer to ranges which can be subsequentlybroken down into subranges as discussed above. Finally, as will beunderstood by one skilled in the art, a range includes each individualmember.

All publications, patent applications, issued patents, and otherdocuments referred to in this specification are herein incorporated byreference as if each individual publication, patent application, issuedpatent, or other document was specifically and individually indicated tobe incorporated by reference in its entirety. Definitions that arecontained in text incorporated by reference are excluded to the extentthat they contradict definitions in this disclosure.

Other embodiments are set forth in the following claims.

What is claimed is:
 1. An electrochromic device comprising: a firstsubstrate that is flexible or rigid and having a first shape, a firstsurface, and a second surface, the second surface comprising a firstconductive material; a second substrate and is flexible and configuredto conform to the shape of the first substrate and having a firstsurface and a second surface, the first surface comprising a secondconductive material; and a sealing member, joining the second surface ofthe first substrate to the first surface of the second substrate forminga chamber therebetween; wherein: the first substrate comprises anultraviolet light absorbing layer; the second surface is coated with afirst polymer-based electrochromic film comprising an anodic material;and the chamber comprises a fluid medium containing a UV-curable gellingagent.
 2. The electrochromic device of claim 1, wherein the frontsurface, the rear surface, or both the front surface and the rearsurface of the second substrate comprises a gas diffusion barrier. 3.The electrochromic device of claim 2, wherein the gas diffusionbarrier(s) comprises a layer applied by plasma-enhanced chemical vapordeposition (PECVD), a layer applied by neutral beam assisted sputtering(NBAS), a layer applied by atomic layer deposition (ALD), a co-polymerof ethylene vinyl alcohol, a polyvinyl alcohol, a polymeric film ofself-assembled nanoparticles (SNAP), a multilayer barrier comprisingalternating layers of organic and inorganic materials, or a multilayerbarrier comprising alternating thin films of cationic and anionicpolymers, or a flexible, thin glass film.
 4. The electrochromic deviceof claim 1, wherein the front surface, the rear surface, or both thefront surface and the rear surface of the first and second substratescomprise an adhesion promotion layer.
 5. The electrochromic device ofclaim 1, wherein the first substrate, the second substrate, or both thefirst substrate and the second substrate comprise polyethylenenaphthalate (PEN), polyacrylonitrile, polyethylene terephthalate (PET),polycarbonate, a cycloolefin polymer (COP), a cycloolefin co-polymer(COC), an acrylic, a polyamide, or an epoxy.
 6. The electrochromicdevice of claim 1, wherein the first conductive material comprises aconductive nanowire coating, a conductive metal mesh, or aninsulator/metal/insulator stack (IMI stack).
 7. The electrochromicdevice of claim 1, wherein the first conductive material comprises afirst conductive nanowire coating, a first conductive metal mesh, or afirst IMI stack; and the second conductive material comprises a secondconductive nanowire coating, a second conductive metal mesh, or a secondIMI stack.
 8. The electrochromic device of claim 7, further comprising aconductive coating overlaying either or both of the first or secondconductive material.
 9. The electrochromic device of claim 8, whereinthe conductive coating comprises a transparent conductive oxide, carbonnanotubes, graphene, or a conductive polymer.
 10. The electrochromicdevice of claim 1, wherein the chamber comprises a first polymer-basedelectrochromic film.
 11. The electrochromic device of claim 1, whereinthe first polymer-based electrochromic film is a first thermoplasticelectrochromic film.
 12. The electrochromic device of claim 10, whereinthe first thermoplastic electrochromic film comprises a firstelectroactive material and a first thermoplastic polymer.
 13. Theelectrochromic device of claim 12, wherein the first electroactivematerial is a cathodic material, and anodic material, or a mixture of acathodic material and an anodic material.
 14. The electrochromic deviceof claim 13, wherein the cathodic material comprises a viologen.
 15. Theelectrochromic device of claim 13, wherein the anodic material comprisesa phenazine, a phenothiazine, a triphenodithiazine, a carbazole, anindolocarbazole, a biscarbazole, or a ferrocene.